New compounds and anion receptors

Abstract

To provide a novel compound that is improved in solubility in organic solvents and can capture anions.SOLUTION: The compound is represented by the general formula (1) in the figure. (In the formula, R1 and R2 each independently represent H, an alkyl group, an aryl group, a heteroaryl group, an alkoxy group or a hydroxy group; and R3 to R6 each independently represent H or an alkyl group.)SELECTED DRAWING: None

Description

[Technical field]

[0001] One embodiment of the present invention relates to novel compounds and anion receptors. [Background technology]

[0002] Anions play important roles in devices, the environment, living organisms, etc., and anion receptors that can recognize and capture these anions are being widely studied because they have various potential applications. The anion receptor can capture free anions contained in a solvent, and can be used in a technique for removing anions from a solvent. For example, in a technique for dissolving a resin in a solvent and applying a resin coating, the anions contained in the solvent may be mixed into the resin coating, which may reduce the physical properties of the resin coating, such as the strength of the resin coating. In addition, anions eluted from the resin raw material into the solvent may adversely affect the formation of the resin coating. Therefore, by adding an anion receptor to the solvent in advance, the action of anions on the resin coating can be reduced. In addition, in cleaning solutions, particularly in fields where high-purity materials are used, it is desirable to remove anions from the cleaning solution in order to reduce the action of anions on the materials. In addition, in electrolytes such as batteries that involve electrochemical action, anions mixed in as impurities may reduce the electrical properties, so it is advisable to add an anion receptor to the electrolyte in advance and remove the anions. In addition, by removing anions from industrial wastewater, the burden on the environment can be reduced.

[0003] Conventionally, there are techniques for removing ions from solvents, such as ion exchange, dialysis, gel permeation, and electrophoresis. These techniques use solvents that have been purified by putting them into a separation device, so they are not techniques for removing anions that are mixed in after purification and before the process in which the solvent is used, or anions that are eluted from solutes added to the solvent. Therefore, there is a demand for the application of materials that can capture anions by adding them during the process or in the product, such as anion receptors. Furthermore, technologies have been developed that can identify and capture anion species using the molecular structure of anion receptors.

[0004] Non-Patent Documents 1 and 2 disclose anion receptors having urea groups at the 8,8'-positions of a 2,2'-binaphthyl group. [Prior art documents] [Non-patent literature]

[0005] [Non-Patent Document 1] S. Kondo, H. Sonoda, T. Katsu, and M. Unno, Sens. Actuators B, 160, 684-690 (2011). [Non-Patent Document 2] S. Kondo, M. Nagamine, S. Karasawa, M. Ishihara, M. Unno, and Y. Yano, Tetrahedron, 67, 943-950 (2011). Summary of the Invention [Problem to be solved by the invention]

[0006] Non-Patent Documents 1 and 2 disclose that anion receptors having the above structure have a relatively rigid skeleton, since the basic skeleton, 2,2'-binaphthyl group, is linked to rigid naphthyl groups via single bonds, and furthermore, since the urea groups introduced at the 8,8'-positions are positioned at appropriate positions, they are capable of capturing anions, and in particular, exhibit selectivity for capturing chloride ions. On the other hand, the anion receptors disclosed in Non-Patent Documents 1 and 2 have a rigid structure due to the 2,2'-binaphthyl group, and therefore tend to have low solubility in organic solvents. In order to capture anions mixed in an organic solvent, it is desirable to dissolve the anion receptor in the organic solvent before use, but the solubility of the anion receptor and the association ability to capture anions tend to be in conflict with each other. Therefore, the development of an anion receptor that satisfies the requirements for solubility and association ability is expected.

[0007] An object of the present invention is to provide a novel compound that has improved solubility in organic solvents and is capable of capturing anions. [Means for solving the problem]

[0008] The present invention relates to the following. [1] A compound represented by the following general formula (1) or the following general formula (2). [ka] (In the general formula (1), R 1 and R 2 each independently represents a hydrogen atom, an alkyl group, an aryl group, a heteroaryl group, an alkoxy group, or a hydroxy group; R 3 ~R 6 each independently represents a hydrogen atom or an alkyl group. [ka] (In the general formula (2), R 1 and R 2 each independently represents a hydrogen atom, an alkyl group, an aryl group, a heteroaryl group, an alkoxy group, or a hydroxy group; R 3 ~R 6 each independently represents a hydrogen atom or an alkyl group; R 7 ~R 14 each independently represents a hydrogen atom or an alkyl group; R 7 or R 8 and R 9 or R 10 may be linked to form a cyclic structure, and / or R 11 or R 12 and R 13 or R 14 may be bonded to form a cyclic structure.)

[0009] [2] In the general formula (1) or (2), R 1 and R 2are each independently an alkyl group having 1 to 8 carbon atoms or an aryl group having 6 to 12 carbon atoms. [3] In the general formula (1) or (2), R 1 and R 2 are each independently an n-butyl group, a tert-butyl group, or a phenyl group. [4] In the general formula (1) or (2), R 1 and R 2 is a tert-butyl group. [5] In the general formula (1) or (2), R 3 ~R 6 is a hydrogen atom.

[0010] [6] Represented by the general formula (2), R 7 or R 8 and R 9 or R 10 and R are bonded to form a ring structure, and / or 11 or R 12 and R 13 or R 14 and are bonded to form a cyclic structure. [7] Represented by the general formula (2), R 7 or R 8 and R 9 or R 10 and R combine to form a benzene ring, and / or 11 or R 12 and R 13 or R 14 and are bonded to form a benzene ring. [8] Represented by the general formula (2), R 7 or R 8 and R 9 or R 10 and R combine to form a benzene ring; 11 or R 12 and R 13 or R 14and are bonded to form a benzene ring. [9] Represented by the general formula (2), R 7 ~R 14 is a hydrogen atom.

[0011]

[10] The compound according to [1], which is any one of the following compounds: [ka] (In the above structural formula, Bu represents an n-butyl group, t-Bu represents a tert-butyl group, and Ph represents a phenyl group.)

[11] An anion receptor comprising a compound according to any one of [1] to

[10] .

[12] A composition comprising the anion receptor according to

[11] and an organic solvent. Effect of the Invention

[0012] According to one embodiment of the present invention, a novel compound that has improved solubility in organic solvents and is capable of capturing anions can be provided. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0013] Hereinafter, one embodiment of the present invention will be described, but the present invention is not limited to the following examples.

[0014] "New compound" The novel compound according to one embodiment is a compound represented by the following general formula (1) or the following general formula (2). [ka]

[0015] In the general formula (1), R 1 and R 2 each independently represents a hydrogen atom, an alkyl group, an aryl group, a heteroaryl group, an alkoxy group, or a hydroxy group; R 3 ~R6 each independently represents a hydrogen atom or an alkyl group.

[0016] [ka]

[0017] In the general formula (2), R 1 and R 2 each independently represents a hydrogen atom, an alkyl group, an aryl group, a heteroaryl group, an alkoxy group, or a hydroxy group; R 3 ~R 6 each independently represents a hydrogen atom or an alkyl group; R 7 ~R 14 each independently represents a hydrogen atom or an alkyl group; R 7 or R 8 and R 9 or R 10 may be linked to form a cyclic structure, and / or R 11 or R 12 and R 13 or R 14 may be bonded to form a cyclic structure.

[0018] This novel compound has improved solubility in organic solvents and can capture anions, and can be suitably used as an anion receptor. In particular, this novel compound can selectively capture chloride ions liberated in organic solvents.

[0019] An anion receptor having a urea group at the 8,8'-position of a 2,2'-binaphthyl group has a rigid structure due to the 2,2'-binaphthyl group and has urea groups at both ends, and therefore has excellent association ability to capture anions. This compound is shown in the following general formula (3). Regarding this molecular structure, the inventors' research has revealed that the substituents introduced into the urea groups at both ends affect the solubility in organic solvents. For example, it has been found that the solubility in organic solvents is higher when the substituent is a tert-butyl group than when the substituent is an n-butyl group. However, there is still room for improvement in the solubility in organic solvents, and in fields where specific organic solvents are preferably used, such as organic devices, it is expected that the solubility in various organic solvents will be further increased.

[0020] [ka] (In general formula (3), R is an n-butyl group, a tert-butyl group, or a phenyl group.)

[0021] The compound represented by general formula (1) has a 5,5',6,6',7,7',8,8'-octahydro-2,2'-binaphthalene skeleton, and by making the ring terminal a cyclohexene ring, it is believed that stacking due to intermolecular π-π interactions in the solid state can be inhibited, and solubility can be improved. The compound represented by general formula (1) has a condensed ring structure of a benzene ring and a cyclohexane ring, so that a rigid structure remains, and the anion association ability can be further increased. Since the 8,8'-position of the 8,8'-substituted 5,5',6,6',7,7',8,8'-octahydro-2,2'-binaphthalene skeleton is a chiral center, the compound represented by the general formula (1) is synthesized as a mixture of two diastereomers. Based on the above structural features, it can be predicted that both of these diastereomers will associate with anions, particularly chloride ions.

[0022] The compounds represented by general formula (2) have a structure in which the binaphthalene skeleton is replaced with an aliphatic or aromatic chain and an ether chain, and are considered to exhibit high solubility due to their flexible structure. On the other hand, due to their flexible structure, their anion association ability tends to decrease. Considering their high solubility in organic solvents, it is possible to efficiently capture anions from organic solvents by adding these compounds to the organic solvent at high concentrations. In addition, the compounds represented by general formula (2) have almost the same positions of the urea groups at both ends as the compounds represented by general formula (1), so they can selectively capture anions, especially chloride ions. Specifically, when the compound represented by general formula (2) is synthesized by coupling 1,2-bis(2-aminophenoxy)ethane, the structure becomes flexible and the solubility improves, but the anion association ability tends to decrease slightly. Furthermore, when the compound represented by general formula (2) is synthesized by coupling with 1,2-bis(2-aminoethoxy)ethane, the structure becomes more flexible and the solubility is remarkably improved, but the anion association ability tends to decrease. From the above viewpoints, anion receptors can be selected and used according to various applications.

[0023] In the general formula (1), R 1 and R 2 each independently represents a hydrogen atom, an alkyl group, an aryl group, a heteroaryl group, an alkoxy group, or a hydroxy group; R 1 and R 2 may be the same or different from each other.

[0024] R 1 and R 2The alkyl group introduced as may be a straight-chain alkyl group or a branched alkyl group, and may be linear or alicyclic. The alkyl group preferably has 1 to 20 carbon atoms, more preferably has 1 to 8 carbon atoms, and even more preferably has 1 to 4 carbon atoms. Examples of the alkyl group include linear alkyl groups such as methyl, ethyl, propyl, isopropyl, n-butyl, tert-butyl, sec-butyl, isobutyl, pentyl, hexyl, heptyl, octyl, isooctyl, 2-ethylhexyl, decyl, and dodecyl; and alicyclic alkyl groups such as cyclopentyl, cyclohexyl, and cycloheptyl, or groups in which at least one hydrogen atom of these groups is substituted with an alkyl group. Among these, linear alkyl groups are preferred, alkyl groups having 1 to 4 carbon atoms are more preferred, and n-butyl or tert-butyl are more preferred.

[0025] R 1 and R 2 The aryl group introduced as the above preferably has 6 to 24 carbon atoms, more preferably has 6 to 12 carbon atoms, and further preferably has 6 to 8 carbon atoms. The aryl group may be a monocyclic, polycyclic, or condensed ring, and may be a group having 1 to 4 aromatic rings or a group having 2 to 4 condensed aromatic rings, and is preferably a group having one benzene ring. Examples of the aryl group include a phenyl group, a naphthyl group, an anthracenyl group, a phenanthrenyl group, a tetracenyl group, a biphenyl group, a terphenyl group, and a fluorenyl group. Among these, a phenyl group is preferred. In these aryl groups, at least one hydrogen atom may be substituted with an alkyl group, and examples thereof include a phenyl group substituted with an alkyl group having 1 to 4 carbon atoms, and specific examples thereof include a p-tolyl group, an m-tolyl group, and an o-tolyl group.

[0026] R 1 and R 2The heteroaryl group introduced as is a group having carbon atoms and heteroatoms on the ring, and examples of the heteroatom include a nitrogen atom, an oxygen atom, a sulfur atom, a silicon atom, a boron atom, and a phosphorus atom. The total number of carbon atoms and heteroatoms in this heteroaryl group is preferably 5 to 24, more preferably 6 to 12, and even more preferably 6 to 8. Examples of this heteroaryl group include groups having a 6-membered heteroaromatic ring such as pyridine and pyrazine, groups having a condensed heteroaromatic ring such as quinoline, isoquinoline, acridine, and phenanthroline, and groups having a 5-membered heteroaromatic ring such as furan, pyrrole, and thiophene.

[0027] R 1 and R 2 The alkoxy group introduced as may be a linear or branched alkyl group, and may be linear or alicyclic. The alkoxy group preferably has 1 to 20 carbon atoms, more preferably 1 to 8 carbon atoms, and even more preferably 1 to 4 carbon atoms. The alkoxy group is represented, for example, as -O-R', where R' represents an alkyl group, and specific examples are as described above for the alkyl group. More preferably, the alkoxy group having 1 to 4 carbon atoms includes a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, an n-butoxy group, a tert-butoxy group, a sec-butoxy group, an isobutoxy group, and the like.

[0028] Preferably, R 1 and R 2 are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 24 carbon atoms, a heteroaryl group having 5 to 24 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or a hydroxy group. More preferably, R 1 and R 2 are each independently a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 12 carbon atoms, a heteroaryl group having 6 to 12 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, or a hydroxy group, and in particular, an alkyl group having 1 to 8 carbon atoms, or a heteroaryl group having 6 to 12 carbon atoms. In one preferred embodiment, R 1and R 2 are each independently an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 8 carbon atoms, and more preferably an n-butyl group, a tert-butyl group, or a phenyl group. 1 and R 2 At least one of R is a tert-butyl group, and more preferably R 1 and R 2 are both tert-butyl groups.

[0029] In the general formula (1), R 3 ~R 6 each independently represents a hydrogen atom or an alkyl group; R 3 ~R 6 may be the same as each other, or may be partially or completely different.

[0030] R 3 ~R 6 The alkyl group introduced as may be a straight-chain alkyl group or a branched alkyl group, and may be linear or alicyclic. The alkyl group preferably has 1 to 20 carbon atoms, more preferably has 1 to 8 carbon atoms, and even more preferably has 1 to 4 carbon atoms. Examples of the alkyl group include linear alkyl groups such as methyl, ethyl, propyl, isopropyl, n-butyl, tert-butyl, sec-butyl, isobutyl, pentyl, hexyl, heptyl, octyl, isooctyl, 2-ethylhexyl, decyl, and dodecyl; and alicyclic alkyl groups such as cyclopentyl, cyclohexyl, and cycloheptyl, or groups in which at least one hydrogen atom of these groups is substituted with an alkyl group. Among these, linear alkyl groups are preferred, alkyl groups having 1 to 4 carbon atoms are more preferred, and methyl or ethyl groups are even more preferred. Preferably, R 3 ~R 6 are each independently a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, even more preferably a hydrogen atom, a methyl group, or an ethyl group, and even more preferably a hydrogen atom. R3 ~R 6 may be partially or completely different, but R 3 ~R 6 It is preferable that at least one of R is a hydrogen atom, and all R 3 ~R 6 It is more preferable that is a hydrogen atom.

[0031] In the compound represented by the general formula (1), R 1 and R 2 are preferably each independently an n-butyl group, a tert-butyl group, or a phenyl group; R 1 and R 2 are each independently an n-butyl group, a tert-butyl group, or a phenyl group, R 3 ~R 6 At least one of R is preferably a hydrogen atom, and all of R 3 ~R 6 It is more preferable that is a hydrogen atom. Specific examples of the compound represented by formula (1) include R 3 ~R 6 is a hydrogen atom, and is represented by the following general formula (1-1). 1 and R 2 are each independently as described in general formula (1).

[0032] [ka]

[0033] Other specific examples of the compound represented by formula (1) include R 1 and R 2 is a tert-butyl group, and R 3 ~R 6 is a hydrogen atom, and is represented by the following general formula (1-2): In the following general formula (1-2), t-Bu represents a tert-butyl group, R 3 ~R 6 are each independently as described in general formula (1).

[0034] [ka]

[0035] In the general formula (2), R 1 and R 2 each independently represents a hydrogen atom, an alkyl group, an aryl group, a heteroaryl group, an alkoxy group, or a hydroxy group, as described above in detail in relation to the general formula (1). In the general formula (2), R 3 ~R 6 each independently represents a hydrogen atom or an alkyl group. Details are as explained above in relation to general formula (1).

[0036] In the general formula (2), R 7 ~R 14 each independently represents a hydrogen atom or an alkyl group; R 7 or R 8 and R 9 or R 10 may be linked to form a cyclic structure, and / or R 11 or R 12 and R 13 or R 14 may be bonded to form a ring structure. 7 ~R 14 may be the same as each other, or may be partially or completely different. R 7 ~R 14The alkyl group introduced as may be a straight-chain alkyl group or a branched alkyl group, and may be linear or alicyclic. The alkyl group preferably has 1 to 20 carbon atoms, more preferably has 1 to 8 carbon atoms, and even more preferably has 1 to 4 carbon atoms. Examples of the alkyl group include linear alkyl groups such as methyl, ethyl, propyl, isopropyl, n-butyl, tert-butyl, sec-butyl, isobutyl, pentyl, hexyl, heptyl, octyl, isooctyl, 2-ethylhexyl, decyl, and dodecyl; and alicyclic alkyl groups such as cyclopentyl, cyclohexyl, and cycloheptyl, or groups in which at least one hydrogen atom of these groups is substituted with an alkyl group. Among these, linear alkyl groups are preferred, alkyl groups having 1 to 4 carbon atoms are more preferred, and methyl or ethyl groups are even more preferred.

[0037] In one example of a novel compound, R 7 ~R 14 may be partially or completely different, but all R 7 ~R 14 is preferably selected from the group consisting of a hydrogen atom and an alkyl group having 1 to 8 carbon atoms, and all of R 7 ~R 14 is more preferably selected from the group consisting of a hydrogen atom, a methyl group, and an ethyl group, and all R 7 ~R 14 It is more preferable that is a hydrogen atom. A compound represented by the following general formula (2-1) is preferred. In the following general formula (2-1), R 1 ~R 6 is as explained in the above general formula (2).

[0038] [ka]

[0039] R 7 or R 8 and R 9 or R 10may be bonded to form a cyclic structure. The cyclic structure preferably has 6 to 24 carbon atoms, more preferably 6 to 12 carbon atoms, and even more preferably 6 to 8 carbon atoms. The cyclic structure may be a monocyclic, polycyclic, or condensed ring, may be aromatic or alicyclic, may have 1 to 4 monocyclic or polycyclic rings, or may have 2 to 4 condensed rings, is preferably an aromatic ring, and more preferably has one benzene ring. 7 ~R 10 Among these, the group not forming a cyclic structure is preferably a hydrogen atom or an alkyl group.

[0040] Similarly, R 11 or R 12 and R 13 or R 14 may be bonded to form a cyclic structure. The cyclic structure preferably has 6 to 24 carbon atoms, more preferably 6 to 12 carbon atoms, and even more preferably 6 to 8 carbon atoms. The cyclic structure may be a monocyclic, polycyclic, or condensed ring, may be aromatic or alicyclic, may have 1 to 4 monocyclic or polycyclic rings, or may have 2 to 4 condensed rings, is preferably an aromatic ring, and more preferably has one benzene ring. 11 ~R 14 Among these, the group not forming a cyclic structure is preferably a hydrogen atom or an alkyl group.

[0041] Examples of the cyclic structure include a structure that can form an arylene group by bonding with the ethylene group between the urea group and the ether bond. Examples of such an arylene group include arylene groups such as a phenylene group, a naphthylene group, and an anthracenylene group, and these arylene groups in which at least one hydrogen atom is substituted with an alkyl group or an aryl group.

[0042] Another example of a novel compound is R 7 ~R 14 may be partially or completely different, but R 7 or R 8 and R 9 or R 10 and form a ring structure, R 11 ~R14 may be a hydrogen atom or an alkyl group, R 11 or R 12 and R 13 or R 14 and form a ring structure, R 7 ~R 10 may be a hydrogen atom or an alkyl group, R 7 or R 8 and R 9 or R 10 and R are bonded to form a ring structure, 11 or R 12 and R 13 or R 14 may be bonded to form a ring structure. 7 or R 8 and R 9 or R 10 and R are bonded to form a ring structure, 11 or R 12 and R 13 or R 14 and form a cyclic structure. In this case, R 7 or R 8 and R 9 or R 10 and a ring structure formed by bonding with R 11 or R 12 and R 13 or R 14 The cyclic structures formed by the bonding of and may be the same or different, but are preferably the same. The cyclic structure formed here is preferably one benzene ring. A compound represented by the following general formula (2-2) is preferred. In the following general formula (2-2), R 1 ~R 6 is as explained in the above general formula (2).

[0043] [ka]

[0044] In the compound represented by the general formula (2), R 1 and R 2are preferably each independently an n-butyl group, a tert-butyl group, or a phenyl group; R 1 and R 2 are each independently an n-butyl group, a tert-butyl group, or a phenyl group, R 3 ~R 6 At least one of R is preferably a hydrogen atom, and all of R 3 ~R 6 It is more preferable that is a hydrogen atom. Specific examples of the compound represented by formula (2) include R 3 ~R 6 is a hydrogen atom, and is represented by the following general formula (2-3). In the general formula (2-3), R 1 and R 2 And R 7 ~R 14 are each independently as described in general formula (2).

[0045] [ka]

[0046] Other specific examples of the compound represented by formula (2) include R 1 and R 2 is a tert-butyl group, and R 3 ~R 6 is a hydrogen atom, and is represented by the following general formula (2-4). In the following general formula (2-4), t-Bu represents a tert-butyl group, R 3 ~R 6 And R 7 ~R 14 are each independently as described in general formula (2).

[0047] [ka]

[0048] Specific novel compounds are listed below. In the structural formulas below, Bu represents an n-butyl group, t-Bu represents a tert-butyl group, and Ph represents a phenyl group.

[0049] [ka]

[0050] Among the above-mentioned novel compounds, compound 1a, compound 1b, and compound 1c are preferred, compound 1a and compound 1b are more preferred, and compound 1b is even more preferred. The above-mentioned novel compounds may be provided as a single compound or as a mixture.

[0051] "Method of compound synthesis" A method for synthesizing the compound represented by general formula (1) or the novel compound represented by general formula (2) will be described below. Note that the novel compound of the present disclosure is not limited to the compound synthesized by the following synthesis method.

[0052] The method for synthesizing the compound represented by general formula (1) can include introducing an isocyanic acid derivative into the amino groups at both ends of 5,5',6,6',7,7',8,8'-octahydro-8,8'-diamino-2,2-binaphthalene. The method for synthesizing the compound represented by the general formula (2) may include introducing an isocyanic acid derivative into a compound represented by the following general formula (4). In the general formula (4), R 7 ~R 14 is as explained in the above general formula (2).

[0053] [ka]

[0054] A specific example of a method for synthesizing a compound represented by general formula (2) can include introducing an isocyanic acid derivative into the amino groups at both ends of 1,2-bis(2-aminophenoxy)ethane or 1,2-bis(2-aminoethoxy)ethane. In any of the compounds, one hydrogen atom in the amino groups at both ends may be substituted. The substituent is R 3 or R 4 The details are as described above.

[0055] The isocyanic acid derivative is a compound represented by R"NCO. R" is R in general formula (1) or general formula (2). 1 or R 2 The group introduced as the above is described in detail. Specifically, the isocyanic acid derivative includes an isocyanic acid alkyl ester, an isocyanic acid aryl ester, and the like. Examples of the isocyanic acid alkyl ester include methyl isocyanate, ethyl isocyanate, propyl isocyanate, isopropyl isocyanate, n-butyl isocyanate, sec-butyl isocyanate, tert-butyl isocyanate, isobutyl isocyanate, pentyl isocyanate, hexyl isocyanate, cyclohexyl isocyanate, and the like. Examples of the isocyanic acid aryl ester include phenyl isocyanate, and the like.

[0056] This reaction can be carried out in various solvents. Examples of usable solvents include ketone solvents such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; alcohol solvents such as methanol, ethanol, isopropanol, ethylene glycol, and diethylene glycol; ether solvents such as diethyl ether, diethylene glycol dimethyl ether, and tetrahydrofuran; amide solvents such as N,N-dimethylformamide and N,N-dimethylacetamide; ester solvents such as ethyl acetate and γ-butyrolactone; and water. After the reaction, the product can be obtained by removing the solvent from the reaction mixture as necessary, and then filtering and drying the product. The product may also be isolated by chromatography for further purification.

[0057] The compound represented by the general formula (1) can be obtained by introducing an isocyanic acid derivative into the amino groups at both ends of 5,5',6,6',7,7',8,8'-octahydro-8,8'-diamino-2,2-binaphthalene. An example of a method for synthesizing 5,5',6,6',7,7',8,8'-octahydro-8,8'-diamino-2,2-binaphthalene is described below. This synthesis method can include synthesizing 7-halogen-1-tetralone using a halogenated benzene as a starting material, coupling the 7-halogen-1-tetralone to synthesize a bis-tetralone, and amminating the ketone group of the bis-tetralone. Chlorobenzene, bromobenzene, etc. can be preferably used as the halogenated benzene. From this starting material, 7-chloro-1-tetralone, 7-bromo-1-tetralone, etc. can be obtained. This synthesis reaction can be carried out with reference to the three-step synthesis method described in MS Newman and S. Seshadri, J. Org. Chem., 1962, 27, 76., CA Kerr, ID Rae, Aust. J. Chem., 1978, 31, 341., etc. In addition, 7-chloro-1-tetralone or 7-bromo-1-tetralone can be synthesized according to a conventional method, and a commercially available product may be used. By coupling 7-halogen-1-tetralone, it is possible to synthesize a bis-tetralone in which two α-tetralones are bonded at the 7-position. This reaction can be carried out in a variety of solvents, and is preferably carried out in a polar solvent such as DMAc (dimethylacetamide). In this synthesis, NiCl 2 Nickel catalysts such as PPh 3 (triphenylphosphine), bipyridine, zinc and other metals and other reaction additives may also be used.

[0058] From the viewpoint of yield, it is preferable to use a reductive amination method as a method for aminating the ketone group of bistetralone. Specifically, the ketone group can be aminated by reacting bistetralone with ammonium formate using an iridium catalyst. As the iridium catalyst, for example, Chloro[N-[4-(dimethylamino)phenyl]-2-pyridinecarboxamidato](pentamethylcyclopentadienyl)iridium(III) ("Ir-PA1 (trade name)" manufactured by Kanto Chemical Co., Ltd.) can be used. This reaction can be carried out in various solvents, and is preferably carried out in a solvent such as ethanol. In this synthesis, a reaction additive such as acetic acid may be used.

[0059] The compound represented by the general formula (2) can be obtained by introducing an isocyanic acid derivative into the amino groups at both ends of 1,2-bis(2-aminophenoxy)ethane or 1,2-bis(2-aminoethoxy)ethane. An example of a method for synthesizing 1,2-bis(2-aminophenoxy)ethane will be described. This method can include synthesizing 1,2-bis(2-nitrophenoxy)ethane using 2-nitrophenol as a starting material, and amminating the nitro groups at both ends of the 1,2-bis(2-nitrophenoxy)ethane. Specifically, 1,2-bis(2-nitrophenoxy)ethane can be obtained by reacting 2-nitrophenol with 1,2-dihalogenethyl. The reaction is preferably carried out in an organic solvent such as dimethylformamide (DMF). 2 CO 3 A catalyst such as may be used. 1,2-bis(2-nitrophenoxy)ethane can be synthesized according to a conventional method, and a commercially available product may be used. The method of aminating the nitro groups at both ends of 1,2-bis(2-nitrophenoxy)ethane may be carried out according to a conventional method, but it is preferable to use a catalytic reduction method. Specifically, the nitro groups can be reduced to amino groups by reducing 1,2-bis(2-nitrophenoxy)ethane with a catalyst such as palladium / carbon (Pd / C) under a reducing atmosphere such as hydrogen gas.

[0060] 1,2-bis(2-aminoethoxy)ethane can be synthesized according to a conventional method, and for example, a commercially available product may be used.

[0061] "Anion receptor" The anion receptor according to one embodiment is characterized in that it contains a compound represented by general formula (1) or general formula (2). Details of the compound represented by general formula (1) and the compound represented by general formula (2) are as described above. Anions play an important role in devices, the environment, living organisms, and the like, and the anion receptor according to one embodiment can be preferably used to recognize and capture these anions. The anion may be a monoatomic ion or a polyatomic ion, and may be a monovalent to tetravalent ion. In particular, the anion receptor according to one embodiment has excellent selectivity for capturing monovalent monoatomic ions or polyatomic ions. Specific examples of the anion include hydride ions (H - ), fluoride ion (F - ), chloride ion (Cl - ), bromide ion (Br - ), iodide ion (I - ), dihydrogen phosphate ion, acetate ion, hydroxide ion, cyanide ion, nitrate ion, nitrite ion, etc. Among these, the anion receptor according to one embodiment has excellent selectivity for capturing halide ions, especially chloride ions.

[0062] The anion receptor may contain one type of compound represented by general formula (1) or general formula (2) alone, or may contain two or more types in combination. The anion receptor preferably contains the above-mentioned compound 1a, compound 1b, compound 1c, or a combination thereof, more preferably contains compound 1a, compound 1b, or a combination thereof, and further preferably contains compound 1b. These compounds have excellent solubility in organic solvents and excellent selectivity for capturing anions, especially chloride ions.

[0063] "composition" A composition according to one embodiment is a composition comprising an organic solvent and an anion receptor, the anion receptor comprising a compound represented by the above-mentioned general formula (1) or general formula (2). This allows anions liberated in the organic solvent to be captured by the anion receptor, providing a composition with a reduced amount of anions. This composition can be applied to electronic or electrical materials in which the inclusion of impurities such as anions is to be avoided, and can be applied to, for example, organic device materials, semiconductor materials, battery materials, etc. In addition, it can be applied to environmental applications such as the treatment of industrial wastewater, biological applications, etc.

[0064] Examples of organic solvents contained in the composition include ketone-based solvents such as acetone, methyl ethyl ketone, and methyl isobutyl ketone, alcohol-based solvents such as methanol, ethanol, isopropanol, ethylene glycol, and diethylene glycol, ether-based solvents such as diethyl ether, diethylene glycol dimethyl ether, and tetrahydrofuran, amide-based solvents such as N,N-dimethylformamide and N,N-dimethylacetamide, ester-based solvents such as ethyl acetate and γ-butyrolactone, aromatic hydrocarbon-based solvents such as benzene, toluene, xylene, mesitylene, tetralin, and diphenylmethane, carbonate-based solvents such as ethylene carbonate, propylene carbonate, fluoroethylene carbonate, dimethyl carbonate, and diethyl carbonate, chloroform, acetonitrile, etc. These organic solvents may be blended in the composition alone or in combination of two or more. The composition may further include additives suitable for various applications. EXAMPLES

[0065] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples.

[0066] The following receptors 1 to 4 were synthesized.

[0067] [ka]

[0068] (Method of synthesizing receptor 1) Receptor 1 represented by the above (1) was synthesized by the method described in Non-Patent Document 1. In the above (1), receptor 1a in which R is a butyl group, receptor 1b in which R is a tert-butyl group, and receptor 1c in which R is a phenyl group could be synthesized.

[0069] (Method of synthesizing receptor 2) The synthetic route to receptor 2 is shown in the following reaction scheme (I).

[0070] [ka]

[0071] 7-Chlorotetralone was synthesized in three steps from chlorobenzene according to the method described in CA Kerr, ID Rae, Aust. J. Chem., 1978, 31, 341.

[0072] In reaction scheme (I), reaction (a) follows the following procedure: A solution of nickel(II) chloride (18 mg), zinc dust (269 mg), triphenylphosphine (192 mg), and 2,2'-bipyridine (21 mg) in N,N-dimethylacetamide (1.2 mL) was stirred at 65°C for 30 minutes under an argon atmosphere. A solution of 7-chloro-1-tetralone (500 mg) in N,N-dimethylacetamide (2.9 mL) was added to the mixture, and the mixture was stirred at 65°C for 12 hours under an argon atmosphere. Ethyl acetate was added, and the mixture was filtered. The filtrate was washed with water and then with brine. The organic layer was dried over anhydrous sodium sulfate, and the solvent was removed under reduced pressure. The residue was recrystallized from a mixed solution of ethyl acetate and hexane to obtain the diketone as a pale yellow solid. Yield: 182 mg, 45%. Mp 188-189 °C. 1 H NMR (500 MHz, CDCl 3 ) δ 8.29 (d, 2H, J = 2.3 Hz), 7.76 (dd, 2H, J 1 = 8.0 Hz, J 2 = 2.3 Hz), 7.35 (d, 2H, J= 8.0 Hz), 3.02 (t, 4H, J= 6.0 Hz), 2.70 (t, 4H, J= 6.6 Hz), 2.18 (tt, 4H, J 1 = 6.6 Hz, J 2 = 6.0 Hz).

[0073] In reaction scheme (I), reaction (b) follows the following procedure: 200 mg of the diketone obtained above, 2 mg (0.005 eq.) of Ir-PA1 (iridium catalyst, obtained from Kanto Chemical Co., Ltd.), 435 mg (10 eq.) of ammonium formate, and 110 μL (4 eq.) of formic acid were placed in a 100 mL two-necked eggplant flask, 7 mL of methanol was poured, and the mixture was refluxed for 14 hours under an argon atmosphere. The solution was evaporated under reduced pressure, and then 15 mL of dichloromethane was added to dissolve the mixture, and the mixture was washed three times with 15 mL of aqueous sodium hydroxide solution (6.7 M). Anhydrous sodium sulfate was added to the obtained organic layer, and the mixture was dried. Then, the mixture was separated by silica gel column chromatography (chloroform:methanol:triethylamine=88:10:2) to obtain the diamine as a brown syrup. Yield: 154 mg, 77%. 1 H NMR (500 MHz, CDCl 3 ) δ 7.64 (s, 2H), 7.39 (dd, 2H, J 1 = 8.0, J 2 = 2.0 Hz), 7.14 (d, 2H, J = 8.0 Hz), 4.04 (t, 2H, J = 5.5 Hz), 2.80 (m, 4H), 2.03 (m, 4H), 1.77 (m, 4H), 1.66 (s, 4H).

[0074] In reaction (c) of reaction formula (I), receptors 2a, 2b, and 2c with various terminals were synthesized using the diamine obtained above according to the following procedure. A solution of 150 mg of diamine and n-butyl isocyanate (130 μL, 2.2 eq.) in ethanol (6 mL) was refluxed under an argon atmosphere for 1.5 hours. The solution was evaporated under reduced pressure, and then separated by silica gel column chromatography (10% methanol-chloroform) to obtain receptor 2a represented by (2a) above as a colorless solid (150 mg, 60%). 1 H NMR (500 MHz, CDCl 3) δ 7.41 (d, 2H, J = 2.0 Hz), 7.31 (dd, 2H, J = 8.0, 1.5 Hz), 7.14 (d, 2H, J = 8.0 Hz), 6.18 (d, 2H, J = 8.5 Hz), 5.70 (t, 2H, J = 6.0 Hz), 4.80 (q, 2H, J = 7.5 Hz), 3.06-2.99 (m, 4H), 2.79-2.66 (m, 4H), 1.87-1.66 (m, 8H), 1.39-1.24 (m, 8H), 0.87 (t, 6H, J = 7.3 Hz) ).

[0075] A solution of 177 mg of diamine and tert-butyl isocyanate (160 μL, 2.2 eq.) in ethanol (4 mL) was refluxed under an argon atmosphere for 3 hours. The solution was evaporated under reduced pressure to obtain receptor 2b (2b) as a colorless solid (181 mg, 61%). 1 H NMR (500 MHz, CDCl 3 ) δ 7.44 (s, 2H), 7.36-7.33 (m, 2H), 7.13 (d, 2H, J = 8.0 Hz), 5.99 (d, 2H, J = 9.0 Hz), 5.58 (d, 2H, J = 8.5 Hz), 4.76 (s, 2H), 2.78-2.67 (m, 4H), 1.95-1.56 (m, 8H), 1.25 (s, 18H).

[0076] A solution of 47 mg of diamine and phenyl isocyanate (40 μL, 2.2 eq.) in ethanol (3 mL) was refluxed under an argon atmosphere for 1 hour. The resulting white precipitate was suction filtered and dried under reduced pressure to obtain receptor 2c represented by (2c) above as a light pink solid (20 mg, 24%). 1 H NMR (500 MHz, CDCl 3) δ 8.25 (s, 2H), 7.46 (s, 2H), 7.35-7.32 (m, 6H), 7.19-7.14 (m, 6H), 6.67-6.83 (m, 2H), 6.51 (d, 2H, J = 8.1 Hz), 4.87-4.84 (s, 2H), 2.78-2.65 (m, 4H), 1.91-1.87 (m, 4H), 1.80-1.73 (m, 4H).

[0077] (Method of synthesizing receptor 3) The synthetic route to receptor 3 is shown in the following reaction scheme (II).

[0078] [ka]

[0079] Starting from 2-nitrophenol, 1,2-bis(2-aminophenoxy)ethane was synthesized by a known method (M. Zuhlke, S. Sass, D. Riebe, T. Beitz, HG Lohmannsroben, ChemPlusChem2017, 82, 1266; A. Contractor, EW Miller, Biochemistry, 2018 57, 237). Subsequently, a solution of 1,2-bis(2-aminophenoxy)ethane (148 mg) and n-butyl isocyanate (132 mg) in ethanol (5 mL) was refluxed overnight under an argon atmosphere. After cooling to room temperature, a colorless solid, receptor 3a (216 mg, 81%) represented by (3a) above was obtained by suction filtration. Mp197-200 °C. 1 H NMR (500 MHz, CDCl 3 ) δ 7.87 (dd, 2H, J 1 = 7.2 Hz, J 2= 2.0 Hz), 7.0-6.98 (m, 4H), 6.94-9.62 (m, 2H), 6.91 (s, 2H), 5.51 (s, 2H), 4.31(s, 4H), 3.20 (q, 4H, J = 7.4 Hz), 1.47 (quint, 4H, J = 7.4 Hz), 1.32 (sext, 4H, J = 7.4 Hz), 0.89 (t, 6H, J = 7.4 Hz). 13 C NMR (126 MHz, CDCl 3 ) δ 156.3, 148.5, 129.6, 123.5, 122.4, 121.9, 113.6, 68.2, 40.1, 32.1, 20.0, 13.8.

[0080] A solution of 1,2-bis(2-aminophenoxy)ethane (321 mg) and tert-butyl isocyanate (290 mg) in ethanol (7 mL) was refluxed overnight under an argon atmosphere. After cooling to room temperature, the mixture was evaporated under reduced pressure. The resulting residue was recrystallized from chloroform / methanol to obtain receptor 3b (443 mg, 76%) represented by (3b) above as a colorless solid. Mp 189-192°C. 1 H NMR (500 MHz, CDCl 3 ) δ 7.88 (dd, 2H, J 1 = 7.2 Hz, J 2 = 2.6 Hz), 6.99-6.90 (m, 6H), 6.86 (s, 2H), 5.31 (s, 2H), 4.30 (s, 4H), 1.34 (s, 18H). 3 C NMR (126 MHz, CDCl 3 ) δ 155.1, 148.1, 130.1, 122.9, 122.5, 121.4, 113.9, 68.5, 50.6, 29.2.

[0081] (Method of synthesizing receptor 4) The synthetic route to receptor 4 is shown in the following reaction scheme (III).

[0082] [ka]

[0083] A solution of 500 mg of 1,2-bis(2-aminoethoxy)ethane (obtained from Tokyo Chemical Industry Co., Ltd.) and n-butyl isocyanate (735 mg) in tetrahydrofuran (5 mL) was refluxed under an argon atmosphere for 14 hours. The solution was evaporated under reduced pressure, and the residue was recrystallized from ethyl acetate to obtain receptor 4a represented by (4a) above as a colorless solid (1.11 g, 95%). Mp 127.5-128.5°C. 1 H NMR (500 MHz, CDCl 3 ) δ 5.31 (s, 2H), 5.17 (s, 2H), 3.62 (s. 4H), 3.58 (t, 4H, J = 5.2 Hz), 3.35 (q, 4H, J = 5.2 Hz), 3.17 (q, 4H, J = 6.9 Hz), 1.47 (quint, 4H, J = 7.4 Hz), 1.35 (sext, 4H, J = 7.4 Hz), 0.92 (t, 6H, J = 7.2 Hz). 13 C NMR (126 MHz, CDCl 3 ) δ 159.0, 70.7, 70.3, 40.5, 40.1, 32.4, 20.1, 13.8.

[0084] A solution of 500 mg of 1,2-bis(2-aminoethoxy)ethane (obtained from Tokyo Chemical Industry Co., Ltd.) and tert-butyl isocyanate (735 mg) in tetrahydrofuran (6 mL) was refluxed under an argon atmosphere for 18 hours. The solution was cooled and the resulting colorless solid was filtered by suction to obtain receptor 4b (804 mg, 69%) represented by (4b) above. Mp 151-156°C. 1 H NMR (500 MHz, CDCl 3) δ 5.46 (s, 2H), 5.15 (s, 2H), 3.75 (s, 4H), 3.56 (t, 4H, J = 4.6 Hz), 3.31 (q, 4H, J = 4.6 Hz), 1.33 (s, 18H). 13 C NMR (126 MHz, CDCl 3 ) δ 158.2, 70.8, 70.2, 50.1, 40.0, 29.5.

[0085] (Method of evaluating solubility) For each receptor, toluene, methyl ethyl ketone (MEK), chloroform (CHCl 3 The solubility in acetonitrile (MeCN) was evaluated. The results are shown in Table 1. The solubilities of receptors 1b, 2, and 3 were quantified using UV-vis spectra. For each receptor, a stock solution was prepared in DMSO (dimethyl sulfoxide), which shows high solubility, and this was added to MeCN using a microsyringe to prepare a dilute MeCN solution. The UV-vis spectra were measured, and the molar extinction coefficients at each wavelength were determined from the UV-vis spectra. For the other solvents, saturated solutions of each receptor were prepared by centrifugation and filtration, and a certain amount of each of these saturated solutions was added to a UV cell containing MeCN, and the UV-vis spectra were measured. The concentrations of each saturated solution were calculated from the UV-vis spectra and the molar extinction coefficients. The solubility of receptor 4 is 1 Quantitative analysis was performed using H NMR. Excessive amounts of receptor 4 were added to each solvent, and the mixture was heated and cooled repeatedly until fully dissolved, after which centrifugation was performed. A fixed amount was weighed out into an NMR tube using a microsyringe, and the solvent was removed under reduced pressure using a rotary evaporator. After drying under reduced pressure using a vacuum pump, a fixed amount of a deuterated chloroform solution containing the weighed naphthalene was added to the NMR tube, and NMR was measured. The saturation concentration was calculated based on the ratio of the integral values.

[0086] The results are shown in Table 1.

[0087] [Table 1]

[0088] This indicates that receptor 1b has low solubility. Receptors 2a, 2b, and 2c are seen to have increased solubility, with receptor 2b being more soluble due to the terminal tert-butyl group. Receptors 3a and 3b also showed improved solubility, with receptor 3b being more soluble due to the terminal tert-butyl group. The solubility of receptors 4a and 4b was also improved, with receptor 4b being more soluble due to the terminal tert-butyl group.

[0089] (Method of evaluating association constant) The association constants for each receptor were evaluated, and the results are shown in Table 2. The anion-associating ability of receptors 1b, 2c, and 3 was evaluated by UV-vis spectrometric titration in acetonitrile (MeCN). The anion-associating ability of receptor 4 was evaluated by 1 The 1H NMR spectroscopy of receptor 2c was performed. The spectral changes due to the conjugated phenyl group were observed, and the association constant was evaluated by nonlinear curve fitting with the theoretical curve for 1:1 association at multiple wavelengths. Receptor 2c accepts acetate anion (AcO - ) and chloride ions (Cl - ) was confirmed. Receptor 2c has a condensed ring structure of a benzene ring and a cyclohexane ring, which leaves a rigid structure and is therefore thought to enhance the association ability of anions. This tendency is also thought to be the same for receptors 2a and 2b, which have the same structure, although this has not been measured. Compared to receptor 1b, receptor 2c's association ability with acetate anions was slightly smaller, but on the same order of magnitude. On the other hand, the association ability with chloride ions was about two orders of magnitude smaller, and a decrease in association ability was observed due to the flexible structure. It was confirmed that all receptors 3 had the ability to associate with acetate ions and chloride ions, but their association ability was about one order of magnitude lower for acetate ions and about two orders of magnitude lower for chloride ions than receptor 1b. This is thought to be due to its flexible structure. It was confirmed that all receptors 4 had the ability to associate with acetate ions and chloride ions, but their association ability was lower than the other receptors. This is thought to be due to receptor 4's flexible structure. Receptors 2c, 3a, 3c, 4a, and 4b tend to have lower association ability than receptor 1b. However, as mentioned above, they have high solubility in various solvents, and therefore, by increasing the concentration of the receptor in the sample, anions can be captured more efficiently.

[0090] [Table 2]

Claims

1. A compound represented by the following general formula (1) or the following general formula (2). 【Chemistry 1】 (In the general formula (1), R １ and R ２ each independently represents a hydrogen atom, an alkyl group, an aryl group, a heteroaryl group, an alkoxy group, or a hydroxy group; R ３ ~R ６ each independently represents a hydrogen atom or an alkyl group. 【Chemistry 2】 (In the general formula (2), R １ and R ２ each independently represents an n-butyl group or a tert-butyl group; R ３ ~R ６ each independently represents a hydrogen atom or an alkyl group; R ７ ~R １４ each independently represents a hydrogen atom or an alkyl group; R ７ Or R ８ and R ９ Or R １０ may be linked to form a cyclic structure, and / or R １１ Or R １２ and R １３ Or R １４ may be bonded to form a cyclic structure.)

2. A compound represented by the general formula (1), wherein R １ and R ２ and each independently represent an alkyl group having 1 to 8 carbon atoms or an aryl group having 6 to 12 carbon atoms.

3. A compound represented by the general formula (1), wherein R １ and R ２ The compound according to claim 1 or 2, wherein each of the groups is independently an n-butyl group, a tert-butyl group, or a phenyl group.

4. In the general formula (1) or (2), R １ and R ２ The compound according to any one of claims 1 to 3, wherein is a tert-butyl group.

5. In the general formula (1) or (2), R ３ ~R ６ The compound according to any one of claims 1 to 4, wherein is a hydrogen atom.

6. A compound represented by the following general formula (2-5): 【Chemistry 2】 (In general formula (2-5), R 1 and R 2 each independently represent a hydrogen atom, an alkyl group, an alkoxy group, or a hydroxy group; R 3 to R 6 each independently represent a hydrogen atom or an alkyl group; R 7 to R 14 each independently represent a hydrogen atom or an alkyl group; R ７ Or R ８ and R ９ Or R １０ and R are bonded to form a cyclic structure, and / or １１ Or R １２ and R １３ Or R １４ and bond to form a ring structure.)

7. In the general formula (2-5), R ７ Or R ８ and R ９ Or R １０ and R are bonded to form a benzene ring, and / or １１ Or R １２ and R １３ Or R １４ and are linked to form a benzene ring.

8. In the general formula (2-5), R ７ Or R ８ and R ９ Or R １０ and R are bonded to form a benzene ring; １１ Or R １２ and R １３ Or R １４ and are linked to form a benzene ring.

9. The compound represented by the general formula (2), wherein R ７ ~R １４ The compound according to claim 1 or 5, wherein is a hydrogen atom.

10. A compound which is any one of the following compounds: 【Chemistry 3】 (In the above structural formula, Bu represents an n-butyl group, t-Bu represents a tert-butyl group, and Ph represents a phenyl group.)

11. An anion receptor comprising the compound according to any one of claims 1 to 10, or a compound represented by the following general formula (2-6): 【Chemistry 2】 (In general formula (2-6), R 1 and R 2 each independently represent a hydrogen atom, an alkyl group, an aryl group, a heteroaryl group, an alkoxy group, or a hydroxy group; R 3 to R 6 each independently represent a hydrogen atom or an alkyl group; R 7 to R 14 each independently represent a hydrogen atom or an alkyl group; R 7 or R 8 may be bonded to R 9 or R 10 to form a cyclic structure, and / or R 11 or R 12 may be bonded to R 13 or R 14 to form a cyclic structure.)

12. A composition comprising the anion receptor of claim 11 and an organic solvent.

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