Methods for synthesizing halide salts

Abstract

General formula: Z n+ X - n The method comprises reacting a first reactant, which is a formate salt, with a diatomic halogen: X 2 with a second reactant which is

Description

[Technical field]

[0001] The present disclosure relates to methods for synthesizing halide salts. [Background technology]

[0002] Among the halide salts, organic halide salts, including halide salts of ammonia derivatives, and inorganic halide salts, including metal halide salts, are known.

[0003] Methods for the synthesis of both organic and inorganic halide salts are constantly being developed with the aim of improving the purity of the products obtained and reducing the consumption of harmful or toxic reagents and solvents. In particular, improving the purity of the synthesized halide salts allows the reduction of post-synthesis processing steps such as extraction, precipitation, filtration, charcoal treatment, distillation, etc.

[0004] High purity halide salts are used in various industrial sectors, for example inorganic halide salts such as lead bromide and organic halide salts such as ammonium halide derivatives, e.g. methylammonium iodide (MAI), are used to synthesize perovskites for photoactive materials used, inter alia, for the production of solar cells.

[0005] Also, from the patent literature, various methods are known for the synthesis of halide salts.

[0006] EP application publication EP3719001 discloses a compound of general formula R x A method for synthesizing organic iodides of NI is described; the method involves synthesizing hydrogen iodide (HI) in situ by mixing molecular iodine with formic acid in a molar ratio of I2:COOH of 1.01:1 or greater; then coupling the synthesized HI with an organic cation:R x N + and introducing a compound that is a donor of 1.01:1 or more. x N +and then maintaining the reaction mixture at a temperature of 20° C. or greater to obtain a compound of the general formula R x The goal of the present invention is to obtain a reaction product that is a salt with NI. By synthesizing HI in the first step of the reaction product and maintaining a specific ratio of reactants, these donors are added to the reaction mixture as formate salts ([R x N + ][HCOO - ]) is prevented from forming by-products. In this way, the product obtained can be purified in a simple and cost-effective manner.

[0007] European Patent Publication EP2072496 describes a method for obtaining pure halide quaternary ammonium salts by reducing the amount of proton acid salts of tertiary amines in the quaternary ammonium salts. The method consists in adding a metal oxide or hydroxide to the quaternary ammonium salt contaminated with the proton acid salts of tertiary amines, and then removing the tertiary amine and water by distillation or heating while introducing nitrogen, argon or air, and the metal salt produced by filtration or column purification.

[0008] In the process for producing halide salts belonging to the group of quaternary amine derivatives, the synthesis typically involves reacting an acid with the respective halide. However, during such synthesis, a part of the basic tertiary amine (organic base) may remain unreacted, which may react with the acid to produce a protonic acid salt, leaving the acid salt as a contaminant in the main product of quaternary ammonium salt. Furthermore, complete removal of the organic base is only possible after the salt of the tertiary amine is decomposed, so deacidification of the product solution is necessary.

[0009] Additionally, preparing a heavy metal halide salt may involve reacting two soluble metal salts, such as a heavy metal nitrate, with an alkali metal halide to form one soluble salt and one insoluble salt that can be removed by precipitation. For example, a lead nitrate solution and a potassium iodide solution can react to produce solid lead iodide, leaving the soluble potassium nitrate in solution. However, the precipitate is typically contaminated with the soluble salt and may therefore require further purification by washing and filtration procedures.

[0010] As mentioned above, many attempts have been made to address the problem of purity of synthesized halide salt.However, despite various approaches to modifying synthesis pathway, known methods do not provide satisfactory effect on the purity of synthesized halide salt due to incomplete conversion of substrate, the need to use certain substrate in excess, or the presence of by-products in the reaction mixture.Therefore, in order to obtain the required purity of halide salt, it is typically necessary to apply laborious and time-consuming post-treatment procedures, which generate additional costs and chemical waste. Summary of the Invention

[0011] There is a need to provide a method for synthesizing halide salts that results in improved purity of the resulting products, thereby limiting the necessary work-up procedures.

[0012] In one embodiment of the present disclosure, a compound of general formula (I): Z n+ X - n Formula I where: X - represents a halogen anion, Z n+ represents a cation having a valence n, 1. A method for synthesizing a halide salt of General formula (II): Z n+ (COOH - )n Formula II The method comprises reacting a first reactant, which is a formate salt of the formula: with a second reactant, which is a diatomic halogen, X2.

[0013] Preferably, the diatomic halogen X2 is selected from Br2 and I2.

[0014] Preferably, the cation (Z n+ ) is Cs + , Ag + , Pb 2+ , Sn 2+ , Bi 3+ , and Sn 4+ is an inorganic cation of a metal selected from the group consisting of:

[0015] Preferably, the cation (Z n+ ) is Pb 2+ It is.

[0016] Alternatively, preferably, the cation (Z n+ ) is represented by the general formula (III), (IV), or (V): [Table 1] is an organic cation of where: R, R 1 , R 2 , R 3 , R 4 each independently represents a hydrogen or an organic substituent moiety, where R 1 , R 2 , R 3 at least one of is not hydrogen; a represents the number of R moieties; A represents a five- or six-membered aliphatic or aromatic hydrocarbon ring, optionally having at least one heteroatom replacing a carbon atom selected from oxygen, nitrogen, and sulfur; Y represents a substituent of ring A other than hydrogen; b represents the number of -Y moieties, where b is zero or an integer ranging from 1 to 4 when A represents a five-membered ring, or b is zero or an integer ranging from 1 to 5 when A represents a six-membered ring.

[0017] Preferably, the organic substituents are R, R 1 , R 2 , R 3 , and R 4 independently for each of C1-C 16 Alkyl, C6 aryl or C 10 Aryl, C 7-26 aralkyl, or heterocyclic substituents.

[0018] Preferably, the organic substituents are R, R 1 , R 2 , R 3 , and R 4 Independently for each of: C1-C 16 C1-C 6 alkyl groups that constitute an acyclic, straight or branched hydrocarbon chain having from 1 to 16 carbon atoms in the chain, optionally containing at least one heteroatom replacing a carbon or hydrogen atom in the alkyl portion. 16 alkyl, where the heteroatoms are selected from the group consisting of phosphorus, silicon, oxygen, nitrogen, sulfur, iodine, chlorine, bromine, and fluorine; C6 aryl or C 10 C6 aryl or C aryls constituting an aromatic monocyclic ring system having 6 carbon atoms forming a ring system or an aromatic bicyclic ring system having 10 carbon atoms forming a bicyclic ring system, optionally with at least one heteroatom replacing a carbon atom or a hydrogen atom in the aryl moiety; 10 aryl, where the heteroatoms are selected from the group consisting of phosphorus, silicon, oxygen, nitrogen, sulfur, iodine, chlorine, bromine, and fluorine; C-C, optionally with at least one heteroatom replacing a carbon or hydrogen atom; 16 C6 aryl or C linked to the nitrogen atom of an organic cation through an alkyl 10 C in the aryl substituent 7-26aralkyl, where the heteroatoms are selected from the group consisting of phosphorus, silicon, oxygen, nitrogen, sulfur, iodine, chlorine, bromine and fluorine; and Heterocyclic substituents constituting a monovalent substituent derived by removing a hydrogen from a five-, six-, or seven-membered saturated or unsaturated alicyclic or aromatic heterocyclic moiety having carbon atoms and one to four ring heteroatoms selected from nitrogen, oxygen, and sulfur. is selected from.

[0019] Preferably, the organic substituents are R, R 1 , R 2 , R 3 and R 4 Independently for each of: C1-C 16 Methyl, ethyl, propyl, isopropyl, n-butyl, tert-butyl, isobutyl, sec-butyl, n-pentyl, isopentyl, neopentyl, methylethyl, diisopropylethyl, 2-methylhexyl, 3-methylheptyl, 2,3-dimethylpentyl, 4-ethyl-2-methyloctyl, 4-isopropylnonyl, hexyl, 2-methylpentyl, 3-methylpentyl, 2,2-dimethylbutyl, and 2,3-dimethylbutyl, 1-methylhexyl, 2-methylhexyl, 1,1-dimethylpentyl, 1,2-dimethylpentyl, 1,3-dimethylpentyl, 2,2-dimethylpentyl, 3-ethyl C1-C butyl ether, 2,2,3-trimethylbutyl, 2-methylheptyl, 3-methylheptyl, 2,3-dimethylhexyl, 3,4-dimethylhexyl, 2,3,4-trimethylpentyl, 3,3-dimethylhexyl, 2,2-trimethylpentyl, 2,4-dimethylhexyl, 2,2,4-trimethylpentyl, 2,3,3-trimethylpentyl, 3,3,4-trimethylpentyl, 3,4,4-trimethylpentyl, 2,4,4-trimethylpentyl, 2-methylheptyl, 3-methylheptyl, 2,3-dimethylhexyl, 3,4-dimethylhexyl, 2,3,4-trimethylpentyl, 3,3-dimethylhexyl, 2,2-trimethylpentyl, 2,4-dimethylhexyl16 alkyl substituents, where the heteroatoms are selected from the group consisting of phosphorus, silicon, oxygen, nitrogen, sulfur, iodine, chlorine, bromine, and fluorine; C6 or C 10 C aryl or C aryl selected from the group consisting of phenyl and naphthyl, optionally with at least one heteroatom replacing a carbon or hydrogen atom in the aryl portion; 10 aryl substituents, where the heteroatoms are selected from the group consisting of phosphorus, silicon, oxygen, nitrogen, sulfur, iodine, chlorine, bromine, and fluorine; C7-, optionally having at least one heteroatom replacing a carbon atom or a hydrogen atom, selected from the group consisting of benzyl, butylphenyl, ethylphenyl, propylphenyl, pentylphenyl, hexylphenyl, ethylnaphthyl, and methylnaphthyl. 26 aralkyl substituents, where the heteroatoms are selected from the group consisting of phosphorus, silicon, oxygen, nitrogen, sulfur, iodine, chlorine, bromine and fluorine; and Heterocyclic substituents selected from the group consisting of furan, tetrahydrofuran, thiophene, diazepine, isoxazole, piperidine, dioxane, pyridine, and pyrimidine. is selected from.

[0020] Preferably, the cation (Z n+ ) has formula (VI), (VII), or (VIII): [Table 2] is an organic cation. Preferably, the method comprises heating the reactants to a temperature of from 25 to 130° C. until a halide salt is obtained.

[0021] Preferably, the reaction of the reactants is carried out in the absence of a solvent.

[0022] Alternatively and preferably, the reaction of the reactants is carried out in the presence of a solvent.

[0023] Preferably, the solvent is selected from the group consisting of water and acetone.

[0024] Preferably, the solvent is selected from the group consisting of water, alcohol, and acetonitrile.

[0025] Preferably, the method further comprises the step of recrystallizing the obtained halide salt.

[0026] Further aspects and features of the present invention are described in the following description of the drawings. [Brief description of the drawings]

[0027] Aspects and features of the present invention will become apparent from the following detailed description of exemplary embodiments thereof when taken in conjunction with the accompanying drawings.

[0028] [Figure 1] 1 provides reactions for methods for synthesizing halide salts according to the present disclosure. [Diagram 2] 1 provides an embodiment of a reaction for a method for synthesizing a halide salt according to the present disclosure. [Diagram 3] 1 presents a method for synthesizing halide salts according to the present disclosure, including the in situ formation and subsequent reaction of formate salts. [Figure 4] 1 presents a 1H-NMR spectrum of methylammonium iodide synthesized according to one of the embodiments. [Diagram 5] 1 presents a 13C-NMR spectrum of methylammonium iodide synthesized according to one of the embodiments. [Figure 6] 1 provides an IR spectrum of methylammonium iodide synthesized according to one of the embodiments. [Figure 7] 1 provides an IR spectrum of methylammonium bromide synthesized according to one of the embodiments. [Figure 8]1 presents a 1H-NMR spectrum of formamidinium iodide synthesized according to one of the embodiments. [Figure 9] 1 presents a 13C-NMR spectrum of formamidinium iodide synthesized according to one of the embodiments. [Figure 10] 1 provides an IR spectrum of formamidinium iodide synthesized according to one of the embodiments. [Figure 11] 1 presents a 1H-NMR spectrum of tetramethylammonium iodide synthesized according to one of the embodiments. [Figure 12] 1 presents a 13C-NMR spectrum of tetramethylammonium iodide synthesized according to one of the embodiments. [Figure 13] 1 provides an IR spectrum of tetramethylammonium iodide synthesized according to one of the embodiments. [Figure 14] 1 presents a 1H-NMR spectrum of tetramethylammonium iodide synthesized according to one of the embodiments. [Figure 15] 1 provides a 13C-NMR spectrum of triethylammonium iodide synthesized according to one of the embodiments. [Figure 16] 1 presents a 13C-NMR spectrum of tetramethylammonium iodide synthesized according to one of the embodiments. [Figure 17] 1 provides an IR spectrum of tetramethylammonium iodide synthesized according to one of the embodiments. [Figure 18] 1 presents a 1H-NMR spectrum of an imidazolium iodide synthesized according to one of the embodiments. [Figure 19] 1 presents a 13C-NMR spectrum of an imidazolium iodide synthesized according to one of the embodiments. [Figure 20] 1 provides an IR spectrum of an imidazolium iodide synthesized according to one of the embodiments. [Figure 21] 1 presents a 1H-NMR spectrum of pyridinium iodide synthesized according to one of the embodiments. [Figure 22] 1 presents a 13C-NMR spectrum of pyridinium iodide synthesized according to one of the embodiments. [Figure 23] 1 provides an IR spectrum of aniline hydroiodide synthesized according to one of the embodiments. [Figure 24] 1 provides a 13H-NMR spectrum of phenylammonium iodide synthesized according to one of the embodiments. [Diagram 25] 1 presents the 1H-NMR spectrum of 3-aminopropionic acid hydroiodide synthesized according to one of the embodiments. [Figure 26] 1 presents a 13C-NMR spectrum of 3-aminopropionic acid hydroiodide synthesized according to one of the embodiments. [Figure 27] 1 provides an IR spectrum of 3-aminopropionic acid hydroiodide synthesized according to one of the embodiments. [Figure 28] 1 presents a 1H-NMR spectrum of N-methylglycine hydroiodide synthesized according to one of the embodiments. [Figure 29] 1 presents a 13C-NMR spectrum of N-methylglycine hydroiodide synthesized according to one of the embodiments. [Diagram 30] 1 provides an IR spectrum of N-methylglycine hydroiodide synthesized according to one of the embodiments. [Diagram 31] 1 presents a 1H-NMR spectrum of glycine hydroiodide synthesized according to one of the embodiments. [Diagram 32] 1 presents a 13C-NMR spectrum of glycine hydroiodide synthesized according to one of the embodiments. [Diagram 33]1 provides an IR spectrum of glycine hydroiodide synthesized according to one of the embodiments. [Diagram 34] 1 presents a 1H-NMR spectrum of benzylammonium iodide synthesized according to one of the embodiments. [Diagram 35] 1 presents a 13C-NMR spectrum of benzylammonium iodide synthesized according to one of the embodiments. [Diagram 36] 1 provides an IR spectrum of benzylammonium iodide synthesized according to one of the embodiments. [Figure 37] 1 provides an X-ray diffraction pattern of PbI2 synthesized according to one of the embodiments. [Figure 38] 1 provides an X-ray diffraction pattern of PbBr2 synthesized according to one of the embodiments. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0029] Reference will now be made to the embodiments, examples of which are illustrated in the accompanying drawings. Aspects and features of the embodiments will be described with reference to the accompanying drawings. However, the present invention may be embodied in many different forms and should not be construed as being limited to only the illustrated embodiments. Rather, these embodiments are provided as examples so that this disclosure will be thorough and complete, and will fully convey the aspects and features of the present invention to those skilled in the art. It should be understood that not all of the features illustrated in the embodiments are essential, and the scope of protection is defined by the features provided in the claims, and not by the literally illustrated embodiments.

[0030] The method for synthesizing halide salts according to the present disclosure comprises the steps of: n+ (HCOO) n The method includes reacting a formate of Z with a diatomic halogen: X2, preferably Br2 or I2, as shown diagrammatically in FIG. n+ (COOH - ) nis a molecular (diatomic) halide X2, an ion:X - and reduced to the general formula Zn n+ (X - ) n whereas the formate ion: HCOO - is converted to gaseous and / or liquid by-products including C, O, and / or H. The reaction by-products are speculated to include CO and / or CO2, and HO and / or H2, and more likely HO. However, due to the volatility of the by-products, the chemical formulas of the by-products are under investigation.

[0031] The reaction can occur by providing a stoichiometric ratio of the substrates. However, formate (Z n+ (COOH - ) n If one of the substrates, either the halogen (X2) or the halide (X2), is provided in excess, the reaction proceeds until the other, insufficient substrate is completely consumed. Thus, to carry out the synthesis of a halide salt, it is not necessary to set any particular restrictions on the ratio of these two substrates, e.g., by converting the halogen X2 into a formate Z n+ (HCOO) n can be added in an amount ranging from 0.5 to 1.2 molar equivalents.

[0032] In order to maintain reasonable reaction times, it is preferable to n+ (COOH - ) n and X2 are heated to a temperature of at least 25° C., preferably at least 60° C. or higher, more preferably the reaction is heated to a temperature between 25 and 130° C., and preferably between 60 and 130° C. For example, Z n+ (COOH - ) n A mixture of Z and X2 can be heated to a temperature such as 25° C., 30° C., 40° C., 50° C., 60° C., 70° C., 75° C., 80° C., 85° C., 90° C., or 95° C., and most preferably 70° C., to obtain a halide salt. During heating, the reactants: Z n+ (COOH - ) nThe mixture of X and X2 can be stirred, e.g., stirred or shaken, to provide an increased level of molecular interaction. However, in the case of smaller amounts of reactants, e.g., on the order of milligrams / milliliters, stirring is not necessary. Stirring of the reactants is preferably carried out throughout the entire reaction duration. Stirring can be carried out for a period of preferably from a few seconds to a few hours, preferably from 1 minute to 4 hours, e.g., from 30 minutes to 1 hour.

[0033] Furthermore, the optimal synthesis conditions and time of the reaction may vary depending on the reactants used. Unless otherwise specified, the solvent or solvent-free conditions, temperature, pressure, and other reaction conditions may be easily selected by those skilled in the art to obtain optimal results for a particular reaction. Optionally, the reaction product may be purified by recrystallization. For example, the reaction product halide salt may be obtained in pure form in liquid or solid state depending on its melting point by simply removing the reaction medium, such as the solvent, if present, under reduced pressure and at a temperature below the boiling point or sublimation point or decomposition point of the obtained halide salt. When the substrates are used in a stoichiometric ratio, both substrates may be completely consumed, which makes it possible to improve the purity of the obtained halide salt without contaminating the product.

[0034] During the course of the reaction, no acids such as hydrohalic acid (HX) are synthesized, and the pH value of the reaction medium remains neutral, about pH = 7, throughout the entire reaction of formate with halide (X2). The reaction of formate with halide (X2) occurs via a free radical mechanism, whereby the halide (X2) is reacted with protons H, which are supplied, for example, with the solvent. + and since the above reaction also results in a halide salt under solvent-free conditions, it is speculated that reduction of the halide:X2 with formate is the preferred reaction regardless of the solvent used. It is further speculated that the solvent molecules, when present in the reaction medium, do not interact with the reactants to form intermediate products or transition states (such as low-energy transition states).

[0035] Substrates and Products The method for synthesis according to the present disclosure comprises the steps of: Z n+ X - n Formula I This makes it possible to obtain halide salts according to the formula: Z n+ represents a cation, which is either an inorganic cation, preferably a cation of a metal, or an organic cation, preferably an ammonium derivative having a positive charge substantially localized at the nitrogen atom; n represents a cation Z n+ where n is preferably equal to 1, 2, 3 or 4; typically n=1 for organic cations, whereby it will be readily apparent from the description of the present disclosure that for inorganic cations n may vary, e.g., 1, 2, 3 or 4.

[0036] X - - halogen ions, preferably Br - or I - It is.

[0037] Organic cation Z n+ Preferably, the organic cation Z of the halide salt n+ is a derivative of an amine, either an aliphatic amine, aromatic amine, aliphatic aromatic amine, or aryl amine, including primary amines, secondary amines, tertiary amines, as applicable; or a derivative of an imine, such as, for example, a formamidinium cation. Halide salts are formed by reacting the above organic cations Z with the above organic cations Z as shown diagrammatically in FIG. n+ from the corresponding formate salt having the formula:

[0038] Preferably, the organic cation (Z n+ ) is represented by the general formula (III), (IV), or (V): [Table 3] is represented by Where: R 1 , R 2 , R3 R, R, provided that at least one of 1 , R 2 , R 3 , R 4 each independently represents hydrogen or an organic substituent; a - represents the number of R moieties on the nitrogen atom, a may be equal to 1 or 2, whereby N + resulting in; A represents a five- or six-membered aliphatic or aromatic hydrocarbon ring, optionally having at least one heteroatom replacing a carbon atom, the heteroatom being preferably selected from oxygen, nitrogen, and sulfur.

[0039] Y represents a substituent other than hydrogen that is a substituent on ring A, where Y is preferably a chemically inert group, i.e., a group that cannot chemically interfere with the formation of the formate salt or the final reaction product, i.e., the halide salt. Preferably, the substituent Y is selected from the group consisting of alkyl, aryl, carboxy, alkoxy, halogen, thiol, hydroxy, trihaloalkyl, and (per)haloalkyl. b represents the number of -Y moieties, where b is zero or an integer ranging from 1 to 4 when A represents a five-membered ring, or b is zero or an integer ranging from 1 to 5 when A represents a six-membered ring.

[0040] As mentioned above, R, R 1 , R 2 , R 3 , R 4 each independently represents hydrogen or an organic substituent, where R 1 , R 2 , R 3 At least one of the groups is not hydrogen; the organic substituents are R, R 1 , R 2 , R 3 , and R 4 Independently for each, preferably: - Linear or branched C1-C 16 C1-C alkyl substituents 16 Hydrocarbon Substituent. As used herein, "C-C16 The term "alkyl," either alone or in combination with other organic substituents, refers to an acyclic, straight- or branched-chain alkyl substituent having from 1 to 16 carbon atoms in the chain; for example, C1-C 16 Alkyl substituents include methyl, ethyl, propyl, isopropyl, n-butyl, tert-butyl, isobutyl, sec-butyl, n-pentyl, isopentyl, neopentyl, methylethyl, diisopropylethyl, 2-methylhexyl, 3-methylheptyl, 2,3-dimethylpentyl, 4-ethyl-2-methyloctyl, 4-isopropylnonyl, hexyl, 2-methylpentyl, 3-methylpentyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 1-methylhexyl, 2-methylhexyl, dimethylpentyl (including the four isomers such as 2,2-dimethylpentyl), 3-ethylpentyl, 2,2,3-trimethylbutyl, 2-methylheptyl, 3-methylheptyl, 2,3-dimethylhexyl, 3,4-dimethylhexyl, 2,3,4-trimethylpentyl, 3,3-dimethylhexyl, 2,2-trimethylpentyl, 2,4-dimethylpentyl, 2,5-dimethylpentyl, 2,6-dimethylpentyl, 2,7-dimethylpentyl, 2,8-dimethylpentyl, 2,9-dimethylpentyl, 2,10-dimethylpentyl, 2,11-dimethylpentyl, 2,12-dimethylpentyl, 2,13-dimethylpentyl, 2,14-dimethylpentyl, 2,15-dimethylpentyl, 2,16-dimethylpentyl, 2,17-dimethylpentyl, 2,18-dimethylpentyl, 2,19-dimethylpentyl, 2,20-dimethylpentyl, 2,21-dimethylpentyl, 2,22-dimethylpentyl, 2,23-dimethylpentyl, 2,24-dimethylpentyl, 2,25-dimethylpentyl, 2,26-dimethylpentyl, 2,27-dimethylpentyl, 2,28-dimethylpentyl, 2,29-dimethylpentyl ethylhexyl, 2,2,4-trimethylpentyl, 2,3,3-trimethylpentyl, 3,3,4-trimethylpentyl, 3,4,4-trimethylpentyl, 2,4,4-trimethylpentyl, 2-methylheptyl (including the 5 isomers such as 2-methylhept-1-yl, 2-methylhept-2-yl, etc.), 3-methylheptyl, 2,3-dimethylhexyl, 3,4-dimethylhexyl, 2,3,4-trimethylpentyl Optionally, C1-C6 may be selected from the group consisting of C1-C6 alkyl, 3,3-dimethylhexyl, 2,2-trimethylpentyl, 2,4-dimethylhexyl, 2,2,4-trimethylpentyl, 2,3,3-trimethylpentyl, 3,3,4-trimethyl-pentyl, 3,4,4-trimethylpentyl, and 2,4,4-trimethylpentyl (including the five isomers such as 2,4,4-trimethylpent-1-yl, 2,4,4-trimethylpent-2-yl, etc.). 16 Alkyl, where applicable, is C1-C 16At least one heteroatom, and preferably 1 to 6 heteroatoms, replacing a carbon atom or a hydrogen atom in the alkyl portion, where the heteroatom is selected from the group consisting of phosphorus, silicon, oxygen, nitrogen, sulfur, iodine, chlorine, bromine, and fluorine; C1-C 16 Non-limiting examples of alkyl are 2,2,2-trifluoroethylamine, 2,2,2-trichloroethylamine, tris(perfluoropropyl)amine. Optionally, C1-C 16 The alkyl can be further substituted with one or more functional groups, such as amino, carboxy, and / or methoxy; - C6 aryl or C 10 Aryl Substituents. As used herein, "C aryl or C 10 The term "aryl", either alone or in combination with other organic substituents, denotes either an aromatic monocyclic ring system containing 6 carbon atoms forming a ring system, or an aromatic bicyclic ring system containing 10 carbon atoms forming a bicyclic ring system; for example, C6 aryl or C 10 The aryl substituent may be selected from the group consisting of phenyl and naphthyl. Optionally, C aryl or C 10 Aryl is C aryl or C 10 At least one heteroatom, and preferably 1 to 6 heteroatoms, replacing a carbon atom or a hydrogen atom in the aryl moiety, where the heteroatom is selected from the group consisting of phosphorus, silicon, oxygen, nitrogen, sulfur, iodine, chlorine, bromine, and fluorine; C6 aryl or C 10 Non-limiting examples of aryl are 4-chlorophenylamine, 2-aminothiophenol, and 4-fluorophenylamine; -C7- 26 Aralkyl Substituents. As used herein, "C 7-26The term "aralkyl" refers to an aryl moiety as defined above, either alone or in combination with other organic substituents, linked (substituted) to the nitrogen atom of a cation via an alkyl moiety, where the term "alkyl" is as defined above; e.g., C7- 27 The aralkyl substituent may be selected from the group consisting of benzyl and butylphenyl. 26 Aralkyl, where applicable, is C7- 26 At least one heteroatom, and preferably 1 to 6 heteroatoms, replacing a carbon atom or a hydrogen atom in the aralkyl moiety, wherein the heteroatom is selected from the group consisting of phosphorus, silicon, oxygen, nitrogen, sulfur, iodine, chlorine, bromine and fluorine; C7- 26 A non-limiting example of an aralkyl is 4-fluoro-phenylethyl-amine; - Heterocyclic Substituents. The term "heterocyclic" as used herein, either alone or in combination with other organic substituents, means a monovalent substituent derived by removing a hydrogen from a five-, six-, or seven-membered saturated or unsaturated heterocyclic ring, including an aromatic heterocyclic ring; the heterocyclic moiety contains carbon atoms and from one to four ring heteroatoms selected from nitrogen, oxygen, and sulfur; for example, a heterocyclic substituent may be selected from the group consisting of furan, tetrahydrofuran, thiophene, diazepine, isoxazole, piperidine, dioxane, pyridine, and pyrimidine. is selected from.

[0041] According to the invention (FIG. 1), the halide salt Z n+ (X - ) to obtain formate Z n+ (HCOO - The organic cations Z used in the compositions n+ Non-limiting examples of include ammonium cations, including alkylammonium cations, dialkylammonium cations, and trialkylammonium cations, amidinium cations, and formamidinium cations; for example, Z n+is methylammonium CH3(H3)N + , Ethylammonium CH3CH2(H3)N + , Propylammonium C3H7(H3)N + , Butylammonium C4H9(H3)N + , Pentylammonium H3C5H 11 N + , Hexylammonium H3C6H 13 N + , Heptylammonium CH 15 (H3)N + Or Octylammonium C8H 17 (H3)N + Cation, formamidinium (H2N-HC=NH2) + , guanidinium (H2N)2-C=NH2) + cation, or acetamidinium cation (H2N-H3CC=NH2) + It can be shown that

[0042] Furthermore, the organic cation Z n+ Non-limiting examples include cations represented by the following formulas (VI), (VII), or (VIII): [Table 4] Thus, the developed method involving the reaction shown in FIG. 1 can be used to prepare ammonium halides such as methyl ammonium halide, dimethyl ammonium halide, propyl ammonium halide, methylethyl ammonium halide, butyl ammonium halide, pentyl ammonium halide, hexyl ammonium halide, heptyl ammonium halide, octyl ammonium halide, formamidinium halide, guanidinium halide, acetamidinium halide, benzyl ammonium halide, benzyl-methyl ammonium halide, phenethyl ammonium halide, N,N-dimethylpropane-1,3-diammonium halide, N,N-diethylethane-1,2-diammonium halide, iso-butyl ammonium halide, iso-propyl ammonium halide, morpholinium halide, phenyl ammonium halide, dimethyl ammonium halide, trimethyl ammonium halide, tetramethyl ammonium halide, di-isopropyl ammonium halide, hexane-1,6-diammonium halide, triethyl ammonium halide, t-butyl ammonium halide, 4 -tert-butyl-phenylammonium halide, butane-1,4-diammonium halide, propane-1,3-diammonium halide, ethane-1,2-diammonium halide, diethylamine halide, N,N-diethylethane-1,2-diammonium halide, cyclohexylethylammonium halide, 2-(phenylene)di(ethylammonium) halide, 4-t-butylbenzylammonium halide, 2-thiophenemethylammonium halide, 2-(4-fluorophenyl)ethylammonium halide, 4-fluorophenyl Fluorobenzyl ammonium halide, 5-aminovaleric acid halide, cyclohexanemethylammonium halide, 2-(4-methoxyphenyl)ethylammonium halide, neopentylammonium halide, 1,4-diazabicyclo[2.2.2]octane halide, N,N-dimethylethylenediamine dihalide, dibutylammonium halide, N,N-diethyl-1,3-propanediamine dihalide, piperazinium dihalide, pyrrolidinium halide, 1,4-phenylenediammonium dihalide, 5-azoniaspiro[4.4]nonane halide, cyclohexylammonium halide, 4-(trifluoromethyl)benzylammonium halide, 2,4,4-trimethylpentane-2-ammonium halide, N,N-dimethyl-1,3-propanediammonium dihalide, dodecylammonium halide, dimethylammonium halide, diethylammonium halide, 1-hexyl-1,4-diazabicyclo[2.2.2]octan-1-ium halide, morpholinium halide, n-octylammonium halide, 4-hydroxyphenethylammonium halide, 4-chlorophenylammonium halide, 4-methoxyphenethylammonium halide, 2-furanmethyl It allows to obtain halide salts, including bromide salts and iodide salts depending on the halide used: Br2, I2, such as ammonium halides, biphenylammonium halides, triphenylammonium halides, 2-thiophenethylammonium halides, diethanolammonium halides, ethanolammonium halides, diphenylammonium halides, 2,2-dipropylmethylpropane-1,3diammonium halides, methoxyethylammonium halides, 2-pyrrolidin-1-ium-1-ylethylammonium halides, quinuclidin-1-ium halides, piperidinium halides, tert-octylammonium halides, etc.

[0043] Inorganic cation Z n+ Preferably, the inorganic cation Z of the halide salt n+ Me + , Me 2+ , Me 3+ and Me 4+ Metal cations such as Me n+ Configure.

[0044] To obtain the halide salt, formate Z n+ (HCOO - ) used as a component of inorganic cation Z n+ Non-limiting examples of Z according to the present invention (FIG. 1) n+ (X - ) is Cs+ , Ag + , Pb 2+ , Sn 2+ , Bi 3+ , and Sn 4+ More preferably, the inorganic cation is selected from the group consisting of Pb 2+ It is.

[0045] Thus, the developed method, including the reactions shown in FIG. 1, makes it possible to obtain halide salts, including bromide and iodide salts depending on the halide used: Br2, I2, such as cesium halides (CsX), silver halides (AgX), lead halides (II) (PbX2), tin (II) halides (SnX2), bismuth (III) halides (BiX3) and tin (IV) halides (SnX4), including CsI, CsBr, AgI, AgBr, PbBr2, PbI2, SnBr2, SnI2, BiBr3, BiI3, SnBr4, SnI4.

[0046] solvent Depending on the nature of the substrate, the reaction may proceed with, for example, the respective formate (Z n+ (HCOO - ) n) can be carried out under solvent-free conditions. FIG. 2 presents an embodiment of the synthesis of halide salts carried out under solvent-free conditions. Methylammonium formate, which is liquid at room temperature, reacts with iodine (I2) (solid) under solvent-free conditions, in an atmosphere of air or under an inert gas (e.g. argon), with heating and stirring to a temperature of 25-130°C. When a stoichiometric ratio of substrates is used, the product obtained under solvent-free conditions can constitute pure methylammonium iodide crystals, by complete consumption of both substrates; however, when the molar ratio of the substrates used is non-stoichiometric, e.g. 1:1, the reaction can be carried out until insufficient substrate is completely consumed. This embodiment thereby shows that solvent molecules are not necessarily required to carry out the reaction. Similar to the reaction of halides with methylammonium formate described above, ethylammonium formate, propylammonium formate, butylammonium formate, or pentylammonium formate can be subjected to the reaction.

[0047] Alternatively, the reaction can be carried out in a solvent environment, for example by dissolving the respective formate (Z n+ (HCOO - ) n ), the solvent allows the substrate molecules to move in the solvent, so that one reactant (Z n+ (HCOO - ) n) with the other reactant (X2). It is also common practice to carry out chemical reactions in a solvent medium, in order to, among other things, improve the stirring of the mixture of reactants and provide better heat transfer in the reaction chamber. The solvent thereby aims to provide the solubility of each of the reactants in order to improve the amount of molecular interaction so as to improve the product yield. Non-limiting examples of solvents that can be used according to the present disclosure include polar solvents, non-polar solvents, organic or inorganic compounds, either protic or aprotic. Furthermore, as a solvent, a mixture of two or more solvent components can be used. Non-limiting exemplary embodiments of solvents, inorganic and organic, respectively, are water, methanol, ethanol, isopropanol, ethers, such as tetrahydrofuran or acetonitrile, or any mixtures thereof, such as ethanol-water mixtures, ethanol-ether mixtures, isopropanol-water mixtures, or acetonitrile-water mixtures. For example, the alcohol solvents can be used in pure form or in the form of mixtures thereof with water, for example in the form of water-alcohol azeotropes, such as a mixture of 95.63 wt% ethanol and 4.37 wt% water. Also, substantially pure ethanol can be used as the organic polar solvent. The amount of the solvent used is not particularly limited. For example, the amount of the solvent can be in the range of 5 to 30 parts by volume (v / W), and preferably, the amount of the solvent can be in the range of 6 to 8 parts by volume (v / W).

[0048] The purpose of the solvent is to provide the desired dissolution of at least one of the reactants, thereby leaving the other reactant (which is not dissolved) suspended in the reaction mixture, or to provide the desired dissolution of both reactants, thereby allowing the desired agitation of the reactants to facilitate their chemical interaction.

[0049] Each formate salt to synthesize the corresponding halide salt: (Z n+ (HCOO - ) n) can be supplied to the reaction chamber in the form of a commercially available product, such as, for example, commercially available ammonium formate, formamidinium formate, methylammonium formate, etc. Alternatively, the respective formate salts: (Z n+ (HCOO - ) n ) can be prepared in situ (in the reaction chamber), for example, by using known methods. An exemplary scheme for synthesizing halide salts containing organic cations according to the present disclosure, including the in situ preparation of salts of formic acid, is shown generally in FIG. y NH 3-y represents an amine compound, which can be, for example, methylamine, which reacts with formic acid (reaction 1) to give the respective salt formate, such as, for example, methylammonium formate: R y NH 3-y + HCO - Following the synthesis of the formate salt, the respective halide X2 is added to the reaction chamber (reaction 2), resulting in the halide salt. Reaction 1 can be carried out in water as a solvent. Alternatively, other solvents such as polar / non-polar organic solvents can be used; or reaction 1 can be carried out in solvent-free conditions.

[0050] Reaction 2 can also be carried out under solvent-free conditions. When both reactions 1 and 2 are carried out solvent-free, the resulting halide salt is already crystalline; this can be preferably done when one of the substrates is liquid at ambient conditions or reaction temperature. Furthermore, when a solvent is present in either reaction 1 or reaction 2, or in both reactions, the resulting halide salt can be obtained by crystallizing the post-reaction mixture.

[0051] There is no particular restriction on the order in reaction 1. For example, primary / secondary / tertiary / quaternary amines can be reacted with formic acid in organic or inorganic polar or non-polar solvents. The amount of amine in reaction 1 ranges from 0.1 molar equivalents to 2.0 molar equivalents relative to formic acid. Furthermore, ammonium formate can be isolated in liquid or solid state. The addition of formic acid to amine is preferably carried out at a temperature ranging from -40°C to 80°C to avoid condensation reactions involving loss of water and amide formation. The polar organic or inorganic solvent in reaction 1 is preferably water, methanol, ethanol, isopropanol, tetrahydrofuran or acetonitrile, and more preferably water. The amount of the organic solvent is not particularly limited, for example, it can be in the range of 5 to 30 parts by volume (v / w), for example, 6 to 8 parts by volume.

[0052] Furthermore, the halogen (X2) in reaction 2 can be added in an amount preferably ranging from 0.5 to 1.2 molar equivalents of the formate, such as 0.5 to 1 molar equivalents. The temperature in the reaction chamber during reaction 2 is preferably maintained in the range of 60° C. to 130° C., for example, the temperature of reaction 2 can be maintained at 60° C., 70° C., 75° C., 80° C., 85° C., 90° C., or 95° C., and more preferably at 70° C. During reaction 2, the reactants were stirred. The duration of reaction 2 can range, for example, from 1 minute to 4 hours, such as 30 minutes to 1 hour, depending on the given formate. The resulting halide salt can be obtained in pure form, in liquid or solid state, by simply removing the reaction medium, such as the solvent, under reduced pressure and at a temperature below the boiling point or sublimation point or decomposition point of the resulting halide salt.

[0053] Embodiment 1 - Synthesis of methylammonium iodide (starting from methylamine): CH3NH3 + I - First, 25.0 ml of formic acid was slowly added to 56.1 ml of methylamine (40 wt% in H2O) under cooling (10°C). The resulting solution was heated to 40°C and 82.3 g of iodine (I2) was slowly added. The product was then heated to 110°C for the time required to remove water. The solid formed was taken up with 50 ml of hot ethanol and subsequently precipitated in excess of cold diethyl ether. The crystals were then collected by filtration; they were washed with diethyl ether and dried in a vacuum oven at 60°C to give 85.79 g of methylammonium iodide (83% yield). 1 H NMR (300MHz, DMSO-d6), d:2,37(s,3H)7.49(s,3H). 13 C NMR (75MHz, DMSO-d6), d:25.00(ppm).

[0054] Figures 4 and 5 present the respective spectra of the products obtained.

[0055] Embodiment 2 - Synthesis of methylammonium iodide (starting from isolated ionic liquid methylammonium formate): CH3NH3 + I - 6 g of methylammonium formate was heated at 100°C. 9.9 g of iodine (I2) was slowly added under vigorous stirring. The precipitate was dissolved in a small amount of hot ethanol and then precipitated in excess of cold diethyl ether. The crystals were then collected by filtration; they were washed with diethyl ether and dried in a vacuum oven at 60°C to give 11 g of methylammonium iodide (89% yield).

[0056] FIG. 6 presents the spectra of each of the products obtained. Embodiment 3 - Synthesis of methylammonium bromide (starting from methylamine): CH3NH3 + Br - 6.86 ml of formic acid was slowly added under cooling (10°C) to 15.46 ml of methylamine (40 wt% in H2O). The resulting solution was further cooled and 1.47 ml (4.6 g) of bromine (Br2) was slowly added. The product was then heated to 110°C to remove water. The solid formed was redissolved in 50 ml of hot ethanol and subsequently precipitated in excess of cold diethyl ether. The crystals were then collected by filtration; they were washed with diethyl ether and dried in a vacuum oven at 60°C to give 15.82 g of methylammonium bromide (79% yield). 1 H NMR (300MHz, DMSO-d6), (s, 3H). 13 C NMR (75 MHz, DMSO-d6) (ppm).

[0057] FIG. 7 presents the IR spectrum of the resulting product (methylammonium bromide).

[0058] Embodiment 4 - Synthesis of methylammonium bromide (starting from isolated ionic liquid methylammonium formate): CH3NH3 + Br - 6 ml of methylammonium formate was cooled at 10°C. 2 ml of bromine (Br2) was added slowly with vigorous stirring. The precipitate was dissolved in a small amount of hot ethanol and then precipitated in excess of cold diethyl ether. The crystals were then collected by filtration; they were washed with diethyl ether and dried in a vacuum oven at 60°C to give 7.2 g of methylammonium bromide (83% yield).

[0059] Embodiment 5 - Synthesis of formamidinium iodide (starting from formamidine acetate): [ka] 5.0 ml of formic acid was added to 6.57 g of formamidine acetate at room temperature. After the solid was completely dissolved, 8.0 g of iodine (I2) was added slowly. The product was then heated to 120°C to remove water. The formed solid was redissolved in 50 ml of hot ethanol and subsequently precipitated in excess of cold diethyl ether. The crystals were then collected by filtration; they were washed with diethyl ether and dried in a vacuum oven at 60°C to give 7.28 g of formamidinium iodide (91% yield). 1 H NMR (300MHz, DMSO-d6), d:----(d,4H)----(quint, 1H). 13 C NMR (75MHz, DMSO-d6), d(ppm).

[0060] Figures 8, 9 and 10 present the respective spectra of the resulting product (formamidinium iodide).

[0061] Embodiment 6 - Synthesis of formamidinium iodide (starting from isolated ionic liquid formamidine formate): [ka] 10 g of formamidine formate was heated at 100°C. 13.5 g of iodine (I2) was slowly added under vigorous stirring. The precipitate was dissolved in a small amount of hot ethanol and then precipitated in excess of cold diethyl ether. The crystals were then collected by filtration; they were washed with diethyl ether and dried in a vacuum oven at 60°C to give 14.7 g of formamidinium iodide (80% yield).

[0062] Embodiment 7 - Synthesis of Tetramethylammonium Iodide (starting from Tetramethylammonium Hydroxide): (CH3)4N + I - 4.80 g of tetramethylammonium hydroxide pentahydrate was weighed and dissolved in 8.0 ml of water. At 10° C., 1.0 ml of formic acid was first added to the solution. The reaction was allowed to proceed at 25° C. for 10 hours. Then, 3.36 g of iodine was added. The mixture was stirred at 70° C. for 12 hours. The reaction solution was cooled to 25° C. The product crystals were then collected by filtration, washed with diethyl ether, and air-dried at 50° C. to give 5.01 g of the title compound (yield 94%). 1 H NMR (600MHz, DMSO-d6), d:3.20(s, 12H). 13 C NMR (150 MHz, DO), d: 55.85. d(ppm).

[0063] Figures 11, 12 and 13 present the respective spectra of the resulting product (tetramethylammonium iodide).

[0064] Embodiment 8 - Synthesis of pyridinium iodide (starting from pyridine): [ka] 2.10 g of pyridine was weighed and mixed with 10 ml of water. At 10° C., 1.0 ml of formic acid was first added to the solution. The mixture was allowed to react at 25° C. for 10 hours. Then, 3.36 g of iodine was added. The mixture was stirred at 70° C. for 12 hours. The reaction solution was cooled to 25° C. Then, 10 ml of ethanol was added, and the mixture was stirred for 10 minutes, followed by the addition of cold diethyl ether. The product crystals were collected by filtration; the crystals were washed with diethyl ether and air-dried at 50° C. to give 4.60 g of pyridinium iodide (86% yield).

[0065] Figures 20, 21 and 22 present the spectra of each of the products obtained (pyridinium iodide).

[0066] Example 9 - Synthesis of imidazolium iodide (starting from imidazole): [ka] 2.70 g of imidazole was weighed and mixed with 12 ml of water. At 10° C., 2.0 ml of formic acid was first added to the solution. The reaction was allowed to proceed at 25° C. for 10 hours. Then, 6.72 g of iodine (I2) was added. The mixture was stirred at 70° C. for 12 hours. The reaction solution was cooled to 25° C. Then, 15 ml of ethanol was added, and the mixture was stirred for 10 minutes, followed by the addition of cold diethyl ether. The product crystals were collected by filtration; the crystals were washed with diethyl ether and air-dried at 50° C. to give 9.88 g of imidazolium iodide (95% yield).

[0067] Figures 17, 18 and 19 present the respective spectra of the resulting products (imidazolium iodide).

[0068] Embodiment 10 - Synthesis of triethylammonium iodide (starting from triethylamine): [ka] 2.14 g of triethylamine was weighed and dissolved in 7 ml of water. At 10° C., 800 ml of formic acid was first added to the solution. The mixture was allowed to react at 25° C. for 10 hours. Then, 2.69 g of iodine (I2) was added. The mixture was stirred at 70° C. for 12 hours. The reaction solution was cooled to 25° C. Then, 9 ml of ethanol was added and stirred for 10 minutes. The product crystals were collected by filtration; the crystals were washed with diethyl ether and air-dried at 50° C. to give 4.23 g of triethylammonium iodide (87% yield).

[0069] Figures 14, 15 and 16 present the respective spectra of the resulting product (triethylammonium iodide).

[0070] Embodiment 11 - Synthesis of aniline hydroiodide (starting from aniline): [ka] 2.47 g of aniline was weighed and dissolved in 8 ml of water. At 10° C., 1 ml of formic acid was first added to the solution. The reaction was allowed to proceed at 25° C. for 10 hours. Then, 3.36 g of iodine (I2) was added. The mixture was stirred at 70° C. for 12 hours. The reaction solution was cooled to 25° C. Then, 10 ml of ethanol was added, and the mixture was stirred for 10 minutes, followed by the addition of cold diethyl ether. The product crystals were collected by filtration; the crystals were washed with diethyl ether and air-dried at 50° C. to give 3.73 g of aniline hydroiodide (64% yield).

[0071] FIG. 23 presents the spectrum of each of the resulting products (aniline hydroiodides).

[0072] Embodiment 12 - Synthesis of benzylamine hydroiodide (starting from benzylamine): [ka] 2.13 g of benzylamine was weighed and dissolved in 8.0 ml of water. At 10° C., 750 ml of formic acid was first added to the solution. The reaction was allowed to proceed at 25° C. for 10 hours. Then, 2.52 g of iodine (I2) was added. The mixture was stirred at 70° C. for 12 hours. The reaction solution was cooled to 25° C. Then, 10 ml of ethanol was added, and the mixture was stirred for 10 minutes, followed by the addition of cold diethyl ether. The product crystals were collected by filtration, washed with diethyl ether, and air-dried at 50° C. to give 5.54 g of benzylamine hydroiodide (89% yield).

[0073] Figures 33, 34 and 35 present the respective spectra of the resulting product (triethylammonium iodide).

[0074] Embodiment 13 -Synthesis of glycine hydroiodide (starting with glycine): [ka] 1.50 g of glycine was weighed and dissolved in 16 ml of water. At 50° C., 2.0 ml of formic acid was first added to the solution. Then, the mixture was reacted at 50° C. for 10 hours. After that, 6.72 g of iodine (I2) was added. The mixture was stirred at 70° C. for 12 hours. The reaction solution was cooled to 25° C. Then, 30 ml of ethanol was added, stirred for 10 minutes, and then cold diethyl ether was added. The product crystals were collected by filtration; the crystals were washed with diethyl ether and air-dried at 50° C. to give 4.63 g of glycine hydroiodide (43% yield).

[0075] Figures 30, 31 and 32 present the respective spectra of the resulting product (3-aminopropionic acid hydroiodide).

[0076] Embodiment 14 -Synthesis of 3-aminopropionic acid hydroiodide (starting from β-alanine): [ka] 1.78 g of β-alanine was weighed and dissolved in 13 ml of water. At 25° C., 2.0 ml of formic acid was first added to the solution. The mixture was allowed to react at 25° C. for 10 hours. Then, 6.72 g of iodine was added. The mixture was stirred at 70° C. for 12 hours. The reaction solution was allowed to cool to 25° C. Then, 25 ml of ethanol was added, stirred for 10 minutes, and then cold diethyl ether was added. The product crystals were collected by filtration, washed with diethyl ether, and air-dried at 50° C. to give 9.68 g of 3-aminopropionic acid hydroiodide (84% yield).

[0077] Figures 24, 25 and 26 present the respective spectra of the resulting product (3-aminopropionic acid hydroiodide).

[0078] Embodiment 15 -Synthesis of N-methylglycine hydroiodide (starting with sarcosine): [ka] 1.78 g of sarcosine was weighed and dissolved in 13 ml of water. At 25° C., 2.0 ml of formic acid was first added to the solution. The reaction was allowed to proceed at 25° C. for 10 hours. Then, 6.72 g of iodine (I2) was added. The mixture was stirred at 70° C. for 12 hours. The reaction solution was cooled to 25° C. Then, 30 ml of ethanol was added, and the mixture was stirred for 10 minutes, followed by the addition of cold diethyl ether. The product crystals were collected by filtration, washed with diethyl ether, and air-dried at 50° C. to give 9.60 g of N-methylglycine hydroiodide (83% yield).

[0079] Figures 27, 28 and 29 present the respective spectra of the resulting product (N-methylglycine hydroiodide).

[0080] Example 16 - Synthesis of lead(II) iodide (starting from lead(II) acetate): 5 g of lead(II) acetate was dissolved in 10 mL of water. Then, 10 mL of formic acid was added, resulting in a colorless precipitate. The intermediate product was filtered and washed with cold water. The wet intermediate product was then dissolved in 170 mL of warm water. Under vigorous stirring, 20 ml of acetone and 4 g of iodine (I2) were slowly added to the solution. The mixture was stirred for an additional 30 min and crystallized to lead(II) iodide (6 g, 85% yield) overnight in the refrigerator.

[0081] FIG. 36 presents the X-ray diffraction patterns of each of the resulting products (lead(II) iodide).

[0082] Example 17 - Synthesis of lead(II) bromide (starting from lead(II) acetate): 5 g of lead(II) acetate was dissolved in 10 mL of water. Then, 10 mL of formic acid was added, resulting in a colorless precipitate. The intermediate product was filtered and washed with cold water. The wet intermediate product was then dissolved in 170 mL of warm water. With vigorous stirring, 20 mL of acetone and 0.8 mL of bromine were slowly added to the solution. The mixture was stirred for an additional 30 minutes and allowed to crystallize into colorless lead(II) bromide (3.5 g, 62% yield) overnight in the refrigerator.

[0083] FIG. 36 presents the X-ray diffraction patterns of each of the resulting products (lead(II) bromide).

Claims

1. General formula (I): Z ｎ＋ X － ｎ Formula I Where: X － represents a halogen anion, Z ｎ＋ represents a cation having a valence n, 1. A method for synthesizing a halide salt of General formula (II): Z ｎ＋ (C�H) － ) ｎ Formula II A first reactant, which is a formate salt of ２ with a second reactant which is

2. The diatomic halogen X ２ Br ２ and I ２ The method of claim 1 , wherein the compound is selected from the group consisting of

3. The cation (Z ｎ＋ ) is Cs ＋ , Ag ＋ , Pb ２＋ , Sn ２＋ , Bi ３＋ , and Sn ４＋ 2. The method of claim 1, wherein the inorganic cation is an inorganic cation of a metal selected from the group consisting of:

4. The cation (Z ｎ＋ ) is Pb ２＋ The method of claim 1, wherein

5. The cation (Z ｎ＋ ) is represented by the general formula (III), (IV), or (V): 【Table 5】 is an organic cation of Where: R, R １ , R ２ , R ３ , R ４ each independently represents a hydrogen or an organic substituent moiety, where R １ , R ２ , R ３ at least one of is not hydrogen; a represents the number of R moieties; A represents a five- or six-membered aliphatic or aromatic hydrocarbon ring, optionally having at least one heteroatom replacing a carbon atom selected from oxygen, nitrogen, and sulfur; Y represents a substituent of A other than hydrogen; b represents the number of -Y moieties, where, when A represents said five-membered ring, b is zero or an integer ranging from 1 to 4, or, when A represents said six-membered ring, b is zero or an integer ranging from 1 to 5; The method according to claim 1 or 2.

6. The organic substituents are R, R １ , R ２ , R ３ , and R ４ Independently for each １ -C １６ Alkyl, C ６ Aryl or C １０ Aryl, C ７－２６ 6. The method of claim 5, wherein the substituent is selected from the group consisting of aralkyl, aryl, and heterocyclic.

7. The organic substituents are R, R １ , R ２ , R ３ , and R ４ Independently for each: C １ -C １６ C which constitutes an acyclic, straight or branched hydrocarbon chain having from 1 to 16 carbon atoms in the chain, optionally with at least one heteroatom replacing a carbon or hydrogen atom in the alkyl portion. １ -C １６ alkyl, where the heteroatoms are selected from the group consisting of phosphorus, silicon, oxygen, nitrogen, sulfur, iodine, chlorine, bromine, and fluorine; C ６ Aryl or C １０ C 1 -C 2 -C 3 -C 4 -C 5 -C 6 -C 7 -C 8 -C 9 -C 10 -C 11 -C 12 -C 13 -C 14 -C 15 -C 16 -C 17 -C 18 -C 19 -C 20 -C 21 -C 22 -C 23 -C 24 -C 25 -C 26 -C 27 -C ６ Aryl or C １０ aryl, where the heteroatoms are selected from the group consisting of phosphorus, silicon, oxygen, nitrogen, sulfur, iodine, chlorine, bromine, and fluorine; Optionally, at least one heteroatom replaces a carbon or hydrogen atom; １ -C １６ C linked to the nitrogen atom of the organic cation through an alkyl ６ Aryl or C １０ C constituting the aryl substituent ７－２６ aralkyl, where the heteroatoms are selected from the group consisting of phosphorus, silicon, oxygen, nitrogen, sulfur, iodine, chlorine, bromine and fluorine; and Heterocyclic substituents which constitute a monovalent substituent derived by removing a hydrogen from a five-, six-, or seven-membered saturated or unsaturated alicyclic or aromatic heterocyclic moiety containing carbon atoms and from one to four ring heteroatoms selected from nitrogen, oxygen, and sulfur The method of claim 5 , wherein the compound is selected from the group consisting of

8. The organic substituents are R, R １ , R ２ , R ３ and R ４ Independently for each: C １ -C １６ Methyl, ethyl, propyl, isopropyl, n-butyl, tert-butyl, isobutyl, sec-butyl, n-pentyl, isopentyl, neopentyl, methylethyl, diisopropylethyl, 2-methylhexyl, 3-methylheptyl, 2,3-dimethylpentyl, 4-ethyl-2-methyloctyl, 4-isopropylnonyl, hexyl, 2-methylpentyl, 3-methylpentyl, 2,2-dimethylbutyl, and 2,3-dimethylbutyl, 1-methylhexyl, 2-methylhexyl, 1,1-dimethylpentyl, 1,2-dimethylpentyl, 1,3-dimethylpentyl, 2,2-dimethylpentyl, 3- C selected from the group consisting of ethylpentyl, 2,2,3-trimethylbutyl, 2-methylheptyl, 3-methylheptyl, 2,3-dimethylhexyl, 3,4-dimethylhexyl, 2,3,4-trimethylpentyl, 3,3-dimethylhexyl, 2,2-trimethylpentyl, 2,4-dimethylhexyl, 2,2,4-trimethylpentyl, 2,3,3-trimethylpentyl, 3,3,4-trimethylpentyl, 3,4,4-trimethylpentyl, 2,4,4-trimethylpentyl, 2-methylheptyl, 3-methylheptyl, 2,3-dimethylhexyl, 3,4-dimethylhexyl, 2,3,4-trimethylpentyl, 3,3-dimethylhexyl, 2,2-trimethylpentyl, 2,4-dimethylhexyl １ -C １６ alkyl substituents, where the heteroatoms are selected from the group consisting of phosphorus, silicon, oxygen, nitrogen, sulfur, iodine, chlorine, bromine, and fluorine; C ６ Or C １０ C selected from the group consisting of phenyl and naphthyl, optionally with at least one heteroatom replacing a carbon or hydrogen atom in the aryl portion; ６ Aryl or C １０ aryl substituents, wherein said heteroatoms are selected from the group consisting of phosphorus, silicon, oxygen, nitrogen, sulfur, iodine, chlorine, bromine, and fluorine; C selected from the group consisting of benzyl, butylphenyl, ethylphenyl, propylphenyl, pentylphenyl, hexylphenyl, ethylnaphthyl, and methylnaphthyl, optionally having at least one heteroatom replacing a carbon atom or a hydrogen atom; ７ - ２６ aralkyl substituents, where the heteroatoms are selected from the group consisting of phosphorus, silicon, oxygen, nitrogen, sulfur, iodine, chlorine, bromine and fluorine; and Heterocyclic substituents selected from the group consisting of furan, tetrahydrofuran, thiophene, diazepine, isoxazole, piperidine, dioxane, pyridine, and pyrimidine. The method of claim 5 , wherein the compound is selected from the group consisting of

9. The cation (Z ｎ＋ ) has the formula (VI), (VII), or (VIII): 【Table 6】 The method according to claim 5, wherein the organic cation is

10. 10. The method of claim 1 comprising heating the first reactant and the second reactant to a temperature of from 25 to 130° C. until the halide salt is obtained.

11. The method of claim 1 , wherein the reaction is carried out in the absence of a solvent.

12. The method of claim 1 , wherein the reaction is carried out in the presence of a solvent.

13. 13. The method of claim 12, wherein the solvent is selected from the group consisting of water and acetone.

14. 13. The method of claim 12, wherein the solvent is selected from the group consisting of water, alcohol, and acetonitrile.

15. 10. The method of claim 1 further comprising the step of recrystallizing the resulting halide salt.

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