Electrochromic compounds and optical articles comprising them

Abstract

The present invention relates to the group of novel electrochromic compounds. More specifically, the present invention relates to azaindole and fused azole compounds substituted with one or several pyridinium rings, and the use of these compounds as variable transmittance media for the manufacture of optical articles, such as ophthalmic lenses.

Description

[0001] This invention relates to the group consisting of novel electrochromic compounds. More specifically, this invention relates to nitrogen-indene compounds and fused azole compounds substituted with one or more pyridinium rings, and the use of these compounds as variable transmittance media in the manufacture of optical articles (such as ophthalmic lenses).

[0002] Electrochromism is a well-known physical phenomenon in which certain types of compounds reversibly change color when a voltage is applied, and this physical phenomenon is observed. Materials undergo reversible changes in their optical properties through oxidation and reduction. Advantageously, electrochromic materials are colorless when no electric field is applied and become colored when an electric field is applied.

[0003] Electrochromic devices, which contain electrochromic compounds, have absorbance that depends solely on the presence of an electric field. Therefore, they can exist in two states: a colored state (when electrically activated) and a faded state (inactive). The optical transmission characteristics of the device depend on the properties of the electrochromic compound.

[0004] There is still a need to improve electrochromic materials so that they can be used as transparent media for forming high-quality articles, especially high-quality ophthalmic lenses, while retaining their electrochromic properties and having a wide color range.

[0005] Surprisingly, the inventors discovered that introducing an azole ring or azoleonium ring into the structure of electrochromic molecules reduces their absorption wavelength in the visible light range. In fact, various azole rings have been introduced, and it has been found that they effectively broaden the wavelength coverage at various activation potentials. This is the case, for example, with substituted imidazolium and fused-ring derivatives, substituted benzimidazolium, and substituted benzo(iso)thiazolium compounds. Furthermore, the viologen molecules of the present invention, or molecules containing nitrogen-indene or fused azoles, have one or both reduction potentials.

[0006] For example, viologen molecules typically exhibit a dicationic structure (bipm) 2+ From single cation (bipm) + ) and from monocations to neutral substances (bipm) 0 The two reduction potentials of ).

[0007]

[0008] From bipm 2+ to bipm + The reaction occurs at the first potential E1 and is reversible, while the reaction from bipm... + to bipm 0 The reaction occurs at a lower potential E2 and is usually irreversible. bipm 0It is considered an unstable compound that can react with oxygen present in the device or with another molecule, resulting in a different chemical structure and also losing its electrochromic properties.

[0009] Here, the inventors have attempted to increase the distance between the two reduction peaks by modifying the chemical structure in order to improve the stability of the device and thus its lifespan. The added chemical groups make the potential distance between the two reduction peaks less than 0.1V, preferably less than 0.3V, and even more preferably less than 0.5V.

[0010] Following extensive research, the inventors have provided novel electrochromic compounds that exhibit excellent electrochromic properties and can be easily incorporated into cells to form, for example, electrochromic lenses.

[0011] Therefore, the compounds of the present invention are advantageously:

[0012] - It is colorless in its inactive state and colored in its active state, such as green, red, purple, blue, yellow or brown;

[0013] - Reversible oxidation or reduction;

[0014] - Easily activated, meaning they have electrochemical potentials ranging from -1.5 to -0.5V; - Stable, meaning they do not produce degradation products.

[0015] More specifically, the compounds of the present invention exhibit a low reversible reduction peak or two separate reversible reduction peaks at least 0.1 V, preferably at least 0.3 V, more preferably at least 0.4 V, and even more preferably at least 0.5 V (the first reversible reduction peak is low).

[0016] The present invention therefore relates to electrochromic compounds having formula (I) as defined below.

[0017] The present invention also relates to an electrochromic composition comprising at least one compound having formula (I).

[0018] Finally, the present invention relates to an electrochromic device, such as an ophthalmic lens, comprising an electrochromic compound having formula (I) or an electrochromic composition according to the present invention.

[0019] definition

[0020] The term "aromatic compound" refers to an unsaturated compound characterized by one or more planar atomic rings linked by covalent bonds.

[0021] The term "cyclic compound" or "ring structure" refers to a compound in which one or more series of atoms are linked together to form a ring. The ring size can vary from three atoms to many atoms, such as five or six atoms, and includes instances where all atoms are carbon (i.e., a carbocyclic ring) or instances where both carbon and non-carbon atoms are present (heterocyclic compounds). More precisely, a "heterocyclic compound or ring structure" is a cyclic compound having atoms of at least two different elements as members of one or more of its rings.

[0022] The term "azole" refers to any five-membered heterocyclic group containing a nitrogen atom and at least one other non-carbon atom as part of a ring. Examples of other non-carbon atoms include nitrogen, oxygen, sulfur, and selenium. The five-membered heterocycle (C5 ring) in this invention is typically an azole. Examples of the azole group include imidazole, pyrazole, oxazole, isoxazole, thiazole, isothiazole, and selenazole.

[0023] The term "conjugated system" refers to a system in which p orbitals with delocalized electrons are connected, which generally lowers the total energy of the molecule and increases its stability. It is conventionally described as having alternating single and multiple bonds. Lone pairs of electrons, free radicals, or carbocations can be part of the system, which can be cyclic, acyclic, linear, or mixed. Conjugated systems according to the invention, formed from five-membered heterocycles (C5 rings) and six-membered (hetero)cycles (C6 rings), are, for example, indene (or benzoxazole), benzisoxazole, benzothiazole, benzimazole, indazole, and imidazo[1,2-a]pyridine.

[0024] The term "pyridinium" refers to the cation of pyridine, in which the nitrogen atom carries a positive charge and is represented by the following formula: Where Y includes C1-C 18 Alkyl, (hetero)aryl, or (hetero)arylalkyl.

[0025] The expression "alkyl" or "C1-C" is used to indicate the alkyl group. 18 "Alkyl" refers to any monovalent group comprising a straight-chain or branched hydrocarbon chain containing 1 to 18 carbon atoms. The expression "C3-C6 alkyl" indicates an alkyl group having 3 to 6 carbon atoms. C1-C 18 Examples of alkyl groups include C1-C4 alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, or tert-butyl; C6-C8 alkyl groups such as n-hexyl, n-heptyl, or n-octyl; and n-pentyl, 2-ethylhexyl, 3,5,5-trimethylhexyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, or n-octadecyl.

[0026] The term "aryl" refers to any monovalent group in an aromatic hydrocarbon containing 6 to 18 carbon atoms, whether monocyclic or polycyclic. The term "polycyclic aryl or polycyclic aromatic compound" refers to a compound in which at least one carbon-carbon bond is shared by two aromatic rings (fused aromatic rings), or a polycyclic aromatic hydrocarbon containing two or more benzene-type rings linked by carbon-carbon single bonds. (C6-C) 18 Examples of aryl groups include phenyl, naphthyl, anthraceneyl, and phenanthrene.

[0027] The term "arylalkyl" refers to any aryl derivative of an alkyl group. The term "arylalkyl" also refers to an aryl group as defined above, bonded to an alkyl group as defined above. Examples of arylalkyl groups include benzyl, phenethyl, phenylpropyl, phenylbutyl, phenylpentyl, phenylhexyl, naphthylmethyl, naphthylethyl, naphthylpropyl, naphthylbutyl, naphthylpentyl, naphthylhexyl, anthracenemethyl, anthraceneethyl, anthracenepropyl, anthracenebutyl, anthracenepentyl, anthracenehexyl, phenanthrenemethyl, phenanthreneethyl, phenanthrenepropyl, phenanthrenebutyl, phenanthrenepentyl, and phenanthrenehexyl.

[0028] The term "heteroaryl" refers to any monovalent group comprising one to three heteroatoms independently selected from oxygen, nitrogen, and sulfur, ranging from 5 to 10 members in a monocyclic or polycyclic aromatic group. (C5-C) 10 Examples of heteroaryl groups include furanyl, thiophene, pyrrole, pyrazolyl, imidazole, isoxazolyl, isothiazolyl, oxazolyl, 1,2,3-triazolyl, 1,2,4-triazolyl, 1-benzofuranyl, 1-benzothiophene, indolyl, benzimidazolyl, inzolyl, 1,2-benzoisooxazolyl, 2,1-benzoisooxazolyl, 1,2-benzoisothiazolyl, 2,1-benzoisothiazolyl, benzothiazolyl, benzooxazolyl, benzotriazolyl, pyridyl, pyridinium, quinolinyl, quinolinium, isoquinolinyl, isoquinolinium, pyridazinyl, terpineyl, phthalazinyl, pyrimidinyl, quinazolinyl, pyrazinyl, and quinoxolinyl.

[0029] Unless otherwise specified, the groups (group and radical) defined above may be unsubstituted or substituted with one or more substituents, such as halogen, alkyl, alkoxy, aryl, heteroaryl, haloalkyl, haloalkoxy, alkoxycarbonyl, alkylacyl, arylacyl, formyl, nitrile, nitro, amide, alkylthio, alkylsulfinyl, alkylsulfonyl, arylthio, arylsulfinyl, arylsulfonyl, amino, alkylamino, arylamino, dialkylamino, and diarylamino.

[0030] These substituents are not phosphonate groups (P=O(OR)(OR'), where R and R' are alkyl or aryl), phosphate groups, carboxyl groups (C=O(OH)), trihalosilyl groups (such as trichlorosilyl), trialkoxysilyl groups (such as triethoxysilyl or trimethoxysilyl), monohalosilyl groups (such as monochlorosilyl) or monoalkoxysilyl.

[0031] Electrochromic compounds

[0032] The electrochromic compounds of the present invention have a central core comprising a five-membered heterocycle (typically a dyzolium ring) fused with a six-membered (hetero)cycle, branched with one or more pyridinium side groups, particularly one, two or three pyridinium side groups.

[0033] Therefore, the electrochromic compound of the present invention is represented by formula (I):

[0034]

[0035] in:

[0036] A is N, + N, N-R1, + N-R1 or C-R1;

[0037] B is C-R2, S, Se, O, N, N-R2 or + N-R2;

[0038] D is C-R3, N, S, O, Se, N-R3 or + N-R3;

[0039] E is C, N, or + N;

[0040] R1 is H, C1-C 18 Alkyl, aryl, or Z;

[0041] R2 is H, C1-C 18 Alkyl, aryl, Z or Z-substituted aryl;

[0042] R3 is H or Cl-C 18 Alkyl, aryl, or Z;

[0043] R4 is H, C1-C 18 Alkyl, aryl, or Z;

[0044] R5 is H, C1-C 18 Alkyl, aryl, or Z;

[0045] R6 is H, C1-C 18 Alkyl, aryl, or Z;

[0046] R7 is H, C1-C 18 Alkyl, aryl, or Z;

[0047] R7 and R6 and / or R6 and R5 and / or R5 and R4 can together form an aromatic ring or heteroaromatic ring fused to the six-membered (hetero)cyclic core (ring C6) to which they are attached, which is optionally substituted with Z.

[0048] Where Z is

[0049] Y is C1-C 18 Alkyl, (hetero)aryl, or (hetero)arylalkyl;

[0050] R8, R9, R 10 and R 11 Independently selected from H and C1-C 18 alkyl;

[0051] R8 and R9 or R 10 and R 11 They can form aromatic rings fused with the pyridinium groups to which they are attached.

[0052] When B = CZ, and when A = + When N, R8 or R 11 It can form aromatic or non-aromatic rings fused with A to form five-membered heterocycles (ring C5) connected to them.

[0053] Choose n to counteract the number of positive charges;

[0054] X is a counter ion;

[0055] Is it a single bond or a double bond?

[0056] This requires the following three prerequisites:

[0057] 1) Ring C5 is a five-membered heterocycle having two independently selected from A, B, D, and E: N, N-R1, + N-R1, N-R2, + N-R2, N-R3 + N-R3, S, Se and O;

[0058] 2) Rings C5 and C6 form a conjugate system; and

[0059] 3) At least one of R1, R2, R3, R4, R5, R6 or R7 is Z, or at least R7 and R6 together form an aromatic ring substituted by Z, or at least R5 and R6 together form an aromatic ring substituted by Z, or at least R5 and R4 together form an aromatic ring substituted by Z.

[0060] In all of the present invention, unless otherwise stated, Y is advantageously C1-C6 alkyl or aryl; for example, Y is methyl, n-hexyl or phenyl.

[0061] In all of the present inventions, counterion X -It can be selected from halide ions, preferably fluoride and chloride ions, tetrafluoroborate, tetraphenylborate, hexafluorophosphate, nitrate, methanesulfonate, trifluoromethanesulfonate, p-toluenesulfonate, hexachloroantimonate, bis(trifluoromethanesulfonyl)imide, perchlorate, acetate and sulfate, preferably X. - It is tetrafluoroborate or hexafluorophosphate.

[0062] The electrochromic compounds of the present invention are typically represented by formulas (II), (III), (IV), (V), (VI), (VII), (VIII), (IX) or (X):

[0063]

[0064]

[0065]

[0066] Among them, A, B, D, E, R1, R2, R3, R4, R5, R6, R7, R8, R9, R 10 and R 11 (When present) and Z, Y, n and X as described above.

[0067] In a preferred embodiment of the invention, the five-membered heterocycle C5 of the central core of the electrochromic compound is an azole ring, and compounds having formulas (I), (II), (III), (IV), (V), (VI), (VII), (VIII), (IX), or (X) are compounds in which:

[0068] -A is N, + N, N-R1 or + N-R1;

[0069] - and / or B is N, N-R2 or + N-R2;

[0070] - and / or D is N, N-R3 or + N-R3.

[0071] Preferred compounds having formulas (I), (II), (III), (IV), (V), (VI), (VII), (VIII), (IX), or (X) may also be such compounds, wherein E is N or + N and / or where D is S.

[0072] Compounds having formula (I) can also be, for example:

[0073] - Such a compound, where A is +N-R1; B is C-R2; D is S or N-R3; E is C, and R1, R2, R3, R4, R5, R7, R8, R9, R 10 R 11 Z, Y, n, and X are defined as above;

[0074] - Such a compound, where A is + N-R1; B is C-R2; D is C-R3; E is N, and R1, R2, R3, R4, R5, R7, R8, R9, R 10 R 11 Z, Y, n, and X are defined as above;

[0075] - Such compounds, where A is N; B is C-R2; D is Se or O; E is C, and R1, R2, R3, R4, R5, R7, R8, R9, R 10 R 11 Z, Y, n, and X are defined as above;

[0076] - Such compounds, where A is C-R1; B is N or + N-R2; D is S; E is C, and R1, R2, R3, R4, R5, R7, R8, R9, R 10 R 11 Z, Y, n, and X are defined as above;

[0077] - Such compounds, where A is C-R1; B is N; D is O; E is C, and R1, R2, R3, R4, R5, R7, R8, R9, R 10 R 11 Z, Y, n, and X are defined as above;

[0078] - Such compounds, where A is C-R1; D is N, + N-R3, S, Se or O; E is C; and R1, R2, R3, R4, R5, R7, R8, R9, R 10 R 11 Z, Y, n, and X are defined as above;

[0079] - Such compounds, where B is N or + N-R2; A is C-R1; D is C-R3; E is N; and R1, R2, R3, R4, R5, R7, R8, R9, R 10 R 11 Z, Y, n, and X are defined as above;

[0080] - Such compounds, where D is +N-R3 or N; A is C-R1; B is C-R2; E is N; and R1, R2, R3, R4, R5, R7, R8, R9, R 10 R 11 Z, Y, n, and X are as defined above; or

[0081] - Such compounds, where E is + N; A is O, S, or Se; B is C-R2; D is C-R3. And R1, R2, R3, R4, R5, R7, R8, R9, R 10 R 11 Z, Y, n and X are defined as above.

[0082] In one variant of the invention, the compounds of the invention are those having formula (II), wherein A is N, + N, N-R1 or + N-R1; D is N-R3. + N-R3, S, Se or O; E is C; and R1, R3, R4, R5, R6, R7, R8, R9, R 10 R 11 Z, Y, n and X are defined as above.

[0083] In one embodiment of this particular variant, the compound having formula (II) is a compound in which A is N. + or + N-R1; D is S; and E is C, and R1, R3, R4, R5, R6, R7, R8, R9, R 10 R 11 Z, Y, n and X are defined as above.

[0084] According to this particular embodiment, the compound can be one of those compounds having formula (II), wherein: A is + N-R1; D is S; E is C; R1 is C1-C 18 Alkyl; preferably, R1 is a C1-C6 alkyl; more preferably, R1 is methyl; R4 is preferably H, C1-C 18 Alkyl or aryl; more preferably, R4 is H; R5 is preferably H, C1-C 18 Alkyl or aryl; more preferably, R5 is H; R6 is preferably H, C1-C 18 Alkyl or aryl; more preferably, R6 is H; R7 is preferably H, C1-C 18 Alkyl or aryl; more preferably, R7 is H; R8 is preferably H, C1-C 18 Alkyl or aryl; more preferably, R8 is H; R9 is preferably H, C1-C 18 Alkyl or aryl; more preferably, R9 is H; R10 The preferred are H, Cl-C 18 Alkyl or aryl; more preferably, R 10 It is H; R 11 The preferred are H, Cl-C 18 Alkyl or aryl; more preferably, R 11 H is preferred; Y is preferably C1-C. 18 Alkyl or aryl; more preferably, Y is a C1-C6 alkyl or aryl; even more preferably, Y is n-hexyl or phenyl; n is 2; and X - It is tetrafluoroborate or hexafluorophosphate, with tetrafluoroborate being preferred.

[0085] Other preferred compounds according to this particular embodiment are typically those having formula (II), wherein A is + N; D is S; E is C; and R8 and A form a saturated or unsaturated five- or six-membered ring fused with the connected ring C5 A and are represented by formula (XI), (XII) or (XIII).

[0086]

[0087] R4, R5, R6, R7, R9, R 10 R 11 Z, Y, n and X are defined as above.

[0088] According to this embodiment, the preferred compound may be one of those compounds having formula (II), wherein A is + N-R1; D is S; E is C; and R1, R4, R5, R6, R7, R8, R9, R 10 R 11 Z, Y, n, and X are as defined above. More specifically, these compounds can be compounds having formula (II), wherein R7 and R6 and / or R6 and R5 and / or R5 and R4 together form an aromatic ring or heteroaromatic ring fused with the (hetero)cyclic core (ring C6) to which they are attached, which is optionally composed of Z, R1, R8, R9, R... as defined above. 10 R 11 , Z, Y, n, and X are replaced. Specific examples are represented as follows:

[0089]

[0090]

[0091] The compound according to this embodiment can also be a compound in which R8 and R9 or R 10 and R 11An aromatic ring fused with the pyridinium groups to which they are attached is formed, and R1, R4, R5, R6, R7, Z, Y, n, and X are as defined above. Examples of such compounds are shown below:

[0092]

[0093] In this particular embodiment, R1 is preferably C1-C 18 Alkyl; more preferably, R1 is a C1-C6 alkyl, such as methyl; R4 is preferably H, C1-C6. 18 Alkyl or aryl; more preferably, R4 is H; R5 is preferably H, C1-C 18 Alkyl or aryl; more preferably, R5 is H; R6 is preferably H, C1-C 18 Alkyl or aryl; more preferably, R6 is H; R7 is preferably H; C1-C 18 Alkyl or aryl; more preferably, R7 is H; R8 is preferably H, C1-C 18 Alkyl or aryl; more preferably, R8 is H; R9 is preferably H, C1-C 18 Alkyl or aryl; more preferably, R9 is H; Y is preferably C1-C 18 Alkyl or aryl; more preferably, Y is C1-C6 alkyl or aryl; even more preferably, Y is phenyl; n is 2; and X - It is tetrafluoroborate or hexafluorophosphate.

[0094] In the second embodiment of this particular variant, the compound having formula (II) is a compound in which A is + N-R1; D is N-R3; E is C; and R1, R3, R4, R5, R6, R7, R8, R9, R 10 R 11 Z, Y, n and X are defined as above.

[0095] According to this particular embodiment, the compound can be one of those compounds having formula (II), where A is + N-R1; D is N-R3; E is C; and R1 is C1-C 18 Alkyl; preferably, R1 is a C1-C6 alkyl group, such as methyl or n-hexyl; R4 is H, C1-C 18 Alkyl or aryl; preferably, R4 is H; R5 is H, C1-C 18 Alkyl or aryl; preferably, R5 is H; R6 is H, C1-C 18 Alkyl or aryl; preferably, R6 is H; R7 is H; C1-C 18 Alkyl or aryl; preferably, R7 is H; R8 is H, C1-C 18Alkyl or aryl; preferably, R8 is H; R9 is H, C1-C 18 Alkyl or aryl; preferably, R9 is H; R 10 It is H, C1-C 18 Alkyl or aryl; preferably, R 10 It is H; R 11 It is H, C1-C 18 Alkyl or aryl; preferably, R 11 H is preferred; Y is preferably C1-C. 18 Alkyl or aryl; more preferably, Y is a C1-C6 alkyl or aryl; even more preferably, Y is methyl, n-hexyl, or phenyl; n is 2; and X - It is tetrafluoroborate or hexafluorophosphate, preferably hexafluorophosphate.

[0096] Other preferred compounds according to this particular embodiment are typically those having formula (II), wherein A is + N-R1; D is N-R3; E is C; R7 and R6 and / or R6 and R5 and / or R5 and R4 together form an aromatic ring or heteroaromatic ring fused with the (hetero)cyclic nucleus (ring C6) to which they are attached, optionally by Z, R1, R3, R8, R9, R as defined above. 10 R 11 The compounds can be substituted with Z, Y, n, and X. Examples of such compounds are shown below:

[0097]

[0098] In this particular embodiment, R1 is preferably C1-C 18 Alkyl; more preferably, R1 is a C1-C6 alkyl, such as methyl; R3 is preferably a C1-C6 alkyl. 18 The alkyl or optionally substituted aryl group, more preferably, R3 is an optionally substituted aryl group, such as 4-tert-butylphenyl; R8 is preferably H, C1-C. 18 Alkyl or aryl; more preferably, R8 is H; R9 is preferably H, C1-C 18 Alkyl or aryl; more preferably, R9 is H; Y is preferably C1-C 18 Alkyl or aryl; more preferably, Y is C1-C6 alkyl or aryl; even more preferably, Y is methyl; n is 4; and X - It is tetrafluoroborate or hexafluorophosphate.

[0099] In the third embodiment of this particular variant, the compound having formula (II) is a compound in which A is N; D is Se; E is C; and R4, R5, R6, R7, R8, R9, R 10 R 11 Z, Y, n and X are defined as above.

[0100] According to this third embodiment, the compound can be one of those compounds having formula (II), wherein: A is N; D is Se; E is C; and R4 is preferably H, Cl-C. 18 Alkyl or aryl; more preferably, R4 is H; R5 is preferably H, C1-C 18 Alkyl or aryl; more preferably, R5 is H; R6 is preferably H, C1-C 18 Alkyl or aryl; more preferably, R6 is H; R7 is preferably H, C1-C 18 Alkyl or aryl; more preferably, R7 is H; R8 is preferably H, C1-C 18 Alkyl or aryl; more preferably, R8 is H; R9 is preferably H, C1-C 18 Alkyl or aryl; more preferably, R9 is H; R 10 The preferred are H, Cl-C 18 Alkyl or aryl; more preferably, R 10 It is H; R 11 The preferred are H, Cl-C 18 Alkyl or aryl; more preferably, R 11 H is preferred; Y is preferably C1-C. 18 Alkyl or aryl; more preferably, Y is a C1-C6 alkyl or aryl; even more preferably, Y is n-hexyl or phenyl; n is 2; and X - It is tetrafluoroborate or hexafluorophosphate.

[0101] In the fourth embodiment of this particular variant, the compound having formula (II) is a compound in which A is N; D is O; E is C; and R4, R5, R6, R7, R8, R9, R 10 R 11 Z, Y, n and X are defined as above.

[0102] According to this fourth embodiment, the compound can be one of those compounds having formula (II), wherein: A is N; D is O; E is C; and R4 is preferably H, Cl-C. 18 Alkyl or aryl; more preferably, R4 is H; R5 is preferably H, C1-C 18 Alkyl or aryl; more preferably, R5 is H; R6 is preferably H, C1-C 18 Alkyl or aryl; more preferably, R6 is H; R7 is preferably H, C1-C 18 Alkyl or aryl; more preferably, R7 is H; R8 is preferably H, C1-C 18 Alkyl or aryl; more preferably, R8 is H; R9 is preferably H, C1-C 18 Alkyl or aryl; more preferably, R9 is H; R 10The preferred are H, Cl-C 18 Alkyl or aryl; more preferably, R 10 It is H; R 11 The preferred are H, Cl-C 18 Alkyl or aryl; more preferably, R 11 H is preferred; Y is preferably C1-C. 18 Alkyl or aryl; more preferably, Y is a C1-C6 alkyl or aryl; even more preferably, Y is n-hexyl or phenyl; n is 2; and X - It is tetrafluoroborate or hexafluorophosphate.

[0103] In a second variant of the invention, the compounds of the invention are those having formula (II), wherein A is + N-R1; D is C-R3; E is N; and R1, R4, R5, R6, R7, R8, R9, R 10 R 11 Z, Y, n and X are defined as above.

[0104] According to this variant, the compound of the present invention can be a compound in which R1 is preferably C1-C 18 Alkyl; more preferably, R1 is a C1-C6 alkyl, such as methyl; R3 is preferably H or C1-C 18 Alkyl group, more preferably, R3 is H; R4 is preferably H, C1-C 18 Alkyl or aryl; more preferably, R4 is H; R5 is preferably H, C1-C 18 Alkyl or aryl; more preferably, R5 is H; R6 is preferably C1-C. 18 Alkyl, aryl, or Z; more preferably, R6 is aryl or Z; R7 is preferably H, C1-C. 18 Alkyl or aryl; more preferably, R7 is H; R8 is preferably H, C1-C 18 Alkyl or aryl; more preferably, R8 is H; R9 is preferably H, C1-C 18 Alkyl or aryl; more preferably, R9 is H; R 10 The preferred are H, Cl-C 18 Alkyl or aryl; more preferably, R 10 It is H; R 11 The preferred are H, Cl-C 18 Alkyl or aryl; more preferably, R 11 H is preferred; Y is preferably C1-C. 18 Alkyl or aryl; more preferably, Y is C1-C6 alkyl or aryl; even more preferably, Y is n-hexyl or phenyl; n is preferably 2 or 3; and X - It is tetrafluoroborate or hexafluorophosphate.

[0105] In a third variant of the invention, the compounds of the invention are those having formula (III), wherein B is N or + N-R2; D is S; E is C; and R2, R4, R5, R6, R7, R8, R9, R 10 R 11 Z, Y, n and X are defined as above.

[0106] According to this third variant of the invention, the compound of the invention can be a compound in which R2, when present, is preferably C1-C. 18 Alkyl, more preferably, R2 is a C1-C6 alkyl, such as methyl; R4 is preferably H, C1-C 18 Alkyl or aryl; more preferably, R4 is H; R5 is preferably H, C1-C 18 Alkyl or aryl; more preferably, R5 is H; R6 is preferably C1-C. 18 Alkyl, aryl; more preferably, R6 is H; R7 is preferably H, C1-C 18 Alkyl or aryl; more preferably, R7 is H; R8 is preferably H, C1-C 18 Alkyl or aryl; more preferably, R8 is H; R9 is preferably H, C1-C 18 Alkyl or aryl; more preferably, R9 is H; R 10 The preferred are H, Cl-C 18 Alkyl or aryl; more preferably, R 10 It is H; R 11 The preferred are H, Cl-C 18 Alkyl or aryl; more preferably, R 11 H is preferred; Y is preferably C1-C. 18 Alkyl or aryl; more preferably, Y is a C1-C6 alkyl or aryl; even more preferably, Y is n-hexyl or phenyl; n is 1 or 2; and X - It is tetrafluoroborate or hexafluorophosphate.

[0107] In a fourth variant of the invention, the compound of the invention is a compound having formula (III), wherein B is N; D is O; E is C; and R2, R4, R5, R6, R7, R8, R9, R 10 R 11 Z, Y, n and X are defined as above.

[0108] According to this fourth variant of the invention, the compound of the invention can be a compound in which R4 is preferably H, C1-C 18 Alkyl or aryl; more preferably, R4 is H; R5 is preferably H, C1-C 18 Alkyl or aryl; more preferably, R5 is H; R6 is preferably C1-C. 18Alkyl, aryl; more preferably, R6 is H; R7 is preferably H, C1-C 18 Alkyl or aryl; more preferably, R7 is H; R8 is preferably H, C1-C 18 Alkyl or aryl; more preferably, R8 is H; R9 is preferably H, C1-C 18 Alkyl or aryl; more preferably, R9 is H; R 10 The preferred are H, Cl-C 18 Alkyl or aryl; more preferably, R 10 It is H; R 11 The preferred are H, Cl-C 18 Alkyl or aryl; more preferably, R 11 H is preferred; Y is preferably C1-C. 18 Alkyl or aryl; more preferably, Y is a C1-C6 alkyl or aryl; even more preferably, Y is n-hexyl or phenyl; n is 1; and X - It is tetrafluoroborate or hexafluorophosphate.

[0109] In a fifth variant of the invention, the compounds of the invention are those having formula (V), wherein A is + N-R1; B is C-R2; D is C-R3; E is N; and R1, R2, R3, R4, R5, R7, R8, R9, R 10 R 11 Z, Y, n and X are defined as above.

[0110] According to this fifth variant of the invention, the compound of the invention can be a compound in which R1 is preferably C1-C 18 Alkyl; more preferably, R1 is a C1-C6 alkyl, such as methyl; R2 is preferably C1-C6. 18 Alkyl or aryl, more preferably, R2 is aryl, such as phenyl; R3 is preferably H, C1-C 18 Alkyl or aryl; more preferably, R3 is H; R4 is preferably H, C1-C 18 Alkyl or aryl; more preferably, R4 is H; R5 is preferably H, C1-C 18 Alkyl or aryl; more preferably, R5 is H; R7 is preferably H, C1-C 18 Alkyl or aryl; more preferably, R7 is H; R8 is preferably H, C1-C 18 Alkyl or aryl; more preferably, R8 is H; R9 is preferably H, C1-C 18 Alkyl or aryl; more preferably, R9 is H; R 10 The preferred are H, Cl-C 18 Alkyl or aryl; more preferably, R 10 It is H; R 11 The preferred are H, Cl-C18 Alkyl or aryl; more preferably, R 11 H is preferred; Y is preferably C1-C. 18 Alkyl or aryl; more preferably, Y is a C1-C6 alkyl or aryl; even more preferably, Y is n-hexyl or phenyl; n is 2; and X - It is tetrafluoroborate or hexafluorophosphate.

[0111] In a sixth variant of the invention, the compounds of the invention are those having formula (IX) or (X), wherein A is N-R1; B is C-R2; D is C-R3; E is N; and R1, R2, R3, R8, R9, R 10 R 11 Z, Y, n and X are defined as above.

[0112] According to this sixth variant of the invention, the compound of the invention can be a compound in which R1 is preferably C1-C 18 Alkyl; more preferably, R1 is a C1-C6 alkyl, such as methyl; R2 is preferably a substituted aryl, more preferably, R2 is 4-tert-butylphenyl or a Z-substituted phenyl; R3 is preferably C1-C6 alkyl. 18 Alkyl or aryl; more preferably, R3 is aryl, such as 4-tert-butylphenyl; R8 is preferably H, C1-C 18 Alkyl or aryl; more preferably, R8 is H; R9 is preferably H, C1-C 18 Alkyl or aryl; more preferably, R9 is H; R 10 The preferred are H, Cl-C 18 Alkyl or aryl; more preferably, R 10 It is H; R 11 The preferred are H, Cl-C 18 Alkyl or aryl; more preferably, R 11 H is preferred; Y is preferably C1-C. 18 Alkyl or aryl; more preferably, Y is a C1-C6 alkyl group, such as methyl; n is 3 or 4; and X - It is tetrafluoroborate or hexafluorophosphate.

[0113] In a particular preferred embodiment of the invention, the compound having formula (I) is selected from the group consisting of the following compounds:

[0114]

[0115]

[0116]

[0117]

[0118] The compound represented by formula (I) can be prepared according to various methods well known in the art.

[0119] For example, the compound represented by formula (I) can be obtained according to the synthetic route detailed below.

[0120] Several routes for obtaining benzimidazole and benzothiazole derivatives have been described; among them, the simplest and most useful routes involve cyclization of the heterocycle with 1,2-phenylenediamine or 2-aminothiophenol, respectively. Synthetic routes involving these precursors have been reviewed. (J. Revuelta, F. Machetti and S. Cicchi, Modern Heterocyclic Chemistry, J. Alvarez-Builla, J.J. Vaquero and J. Barluenga, eds., Wiley-WCH Publishers, Weinheim, 2011, Vol. 2, pp. 809-923.)

[0121] Although 2-(hetero)arylbenzothiazole can be obtained via a tandem acylation-cyclization dehydration sequence of 2-aminobenzylthiophenol, other routes are known. For example, 2-(4-pyridyl)benzothiazole is first obtained by the high-temperature reaction of 4-methylpyridine with sulfur in the presence of aniline, or by isonicotinic acid and 2-aminobenzylthiophenol in the presence of thionyl chloride. Furthermore, the same compound can be obtained by the cyclization condensation of 2-aminobenzylthiophenol with pyridine-4-carboxaldehyde and the subsequent oxidation of the resulting benzothiazoline with ferric(III) sulfate (PEMiller, GLOliver, JRDann and JWGates Jr., J.Org.Chem., 1957, 22, 664). Recently, it has been shown that benzothiazoles can also be obtained from aldehydes or alkanophenones and 2-aminothiophene; the oxidation step is carried out by air oxidation in DMSO (Y. Liao, H. Qi, S. Chen, P. Jiang, W. Zhou and G.-J. Deng, Org. Lett. [Organic Letters], 2012, 14, 6004). A combination of these methods was used in this work, wherein an ethanolic solution of 2-aminothiophene and pyridine-4-carboxaldehyde was stirred in air. The pyridine moiety was then N-alkylated with a haloalkane (e.g., 1-iodohexane) as expected, which proceeded as readily as expected (K. Halman and OH Hankovszky, Acta Chim. Acad. Sci. Hung., 1965, 43, 263; P. Zavins, E. Slavinowski and A. Arens, Khim. Geterotsikl. Soedin., 1973, 104). Therefore, 1-iodohexane provides iodide salts in good yields and ultimately tetrafluoroborate following anion exchange. The latter can then be further alkylated at N-3 of the benzothiazole moiety with methyl toluenesulfonate, as shown in Scheme 1.

[0122]

[0123] Although 2-(1-phenylpyridin-4-yl-1-onium)benzothiazole has been synthesized using the convoluted sequence of pyranium salt chemistry (GNDorofeenko, AVKoblik, BATertov, and TIPolyakova, Khim. Geterotsikl. Soedin., 1973, 1016), a simpler method for obtaining this compound and its derived salts is described in Scheme 6. The key steps involve the partial N-arylation of pyridine with readily available diphenyliodonium trifluoromethanesulfonate under copper catalysis (M. Bielawski and B. Olofsson, Chem. Commun. [Chemical Communications], 2007, 2521). This method has been used for the N-phenylation of a range of other heterocyclic systems (T. Lv, Z. Wang, J. You, J. Lan and G. Gao, J. Org. Chem., 2013, 73, 5723; C. Reus, M. Stolar, J. Vanderkley, J. Neubauer and T. Baumgartner, J. Am. Chem. Soc., 2015, 137, 11710). Benzothiazoles were directly alkylated using methyl toluenesulfonate.

[0124]

[0125] Similar sequences to those depicted in Schemes 1 and 2 apply to readily available quinoline-4-carboxaldehyde (W.-Z.Weng, J.-S.Guo, K.-X.Liu, T.-Q.Shao, L.-Q.Song, Y.-P.Zhu, Y.-Y.Sun and Q.-G.Meng, Can.J.Chem., 2020, 98, 179) and the derived benzothiazole.

[0126] Although both 2-(2-pyridyl)-benzimidazole and 2-(4-pyridyl)-benzimidazole are readily available from o-phenylenediamine (OPD) and carboxylic acid derivatives, condensation-air oxidation of OPD with appropriate pyridinecarboxaldehyde is efficiently achieved (see S. Haneda, Z. Gan, K. Eda and M. Hayashi, Organometallics, 2007, 26, 6551). 2-(4-pyridyl)benzimidazole can be selectively methylated in the imidazole ring by treatment with MeI under basic conditions. Sequential alkylation of the pyridine moiety and the benzimidazole ring is then carried out. In a similar manner to that employed previously, Cu-mediated N-arylation of the pyridine moiety in 1-methyl-2-(4-pyridyl)benzimidazole with diphenyliodonium trifluoromethanesulfonate, followed by treatment with haloalkanes or MeOTs, provides a series of novel compounds (Scheme 3).

[0127]

[0128] Imidazolo[1,2-a]pyridine can be obtained via multiple routes, and numerous reviews on the synthesis and chemistry of these compounds are available (HLBlewitt, Special Topics in Heterocyclic Chemistry, edited by A. Weissberger and E.T. Cayllor, Wiley-Interscience, New York, 1977, pp. 117-178; F. Couty and G. Evano, Comprehensive Heterocyclic Chemistry). III [Comprehensive Heterocyclic Chemistry III], eds. A.R. Katritzky, C.R. Camsden, E.F. V. Criven, and R.J. K. Taylor, Elsevier, Oxford, 2008, Vol. 11, pp. 409-499; A.B. Agdi, S. Santra, K. Monir, and A. Hajra, Chem. Commun. [Chemical Communications], 2015, 51, 1555; S.R. Oopan, S.M. Patil, and J. Palaniraja, Res. Chem. Intermed. [Studies in Chemical Intermediates], 2016, 42, 2740. To date, the most useful entries for these bicyclic compounds include the N-alkylation-cyclization condensation of 2-aminopyridine with α-bromoketones. Therefore, commercially available 2-amino-4-bromopyridine was reacted with benzoylmethyl bromide in methanol in the presence of NaHCO3 to provide 7-bromo-2-phenylimidazo[1,2-a]pyridine A [KCLLee and ETSun, PCT WO 2006 / 101455A1 (2006)]. A similar reaction, in which 4-(bromoacetyl)pyridine hydrobromide (MPHay, S. Turcette, JUFlannagan, M. Bonnet, D.A.C.H., P.D.Sutphin, P.N. Guyen, A.J. Graccia, and W.D.A.D.N., J.M.C. Chem. [Journal of Medicinal Chemistry], 2010, 53, 787) was substituted for benzoylmethyl bromide, to provide 7-bromo-2-(4-pyridyl)imidazo[1,2-a]pyridine B in good yield. The Suzuki-Miyaura coupling of A with 4-(4,4,5,5-tetramethyl-1,3,2-dioxaborhexacyclopentan-2-yl)pyridine provides 2-phenyl-7-(4-pyridyl)imidazo[1,2-a]pyridine C in high yield. Using this Pd coupling reaction with B, a 7-phenyl derivative D and a bispyridyl compound E are produced. Alkylation of C and D on a pyridine nitrogen in MeCN with 1-iodohexane yields salts F and G, respectively.Further alkylation of F and G is completed at N-1 by heating with methyl toluenesulfonate. Dialkylation of the two pyridine moieties in E can be achieved by heating with an excess of alkyl halide to provide H, which can also be methylated at N-1 with methyl toluenesulfonate (Scheme 4).

[0129]

[0130] 4,4'-Dibromodiphenylethylenedione is widely commercially available, and its isomers, dibromophenanthrene-9,10-dione and 3,6-dibromophenanthrene-9,10-dione (MOBaniKhaled, J.D. Mottishaw, H. Sun, Cryst. Growth), are also available. Des. [Crystal Growth and Design], 2015, 15, 2235; A. Patel, SY Sharp, K. Hall, W. Lewis, MFG Stevens, P. Workman, CJ Moody, Org. Biomol. Chem. [Organic and Biomolecular Chemistry], 2016, 14, 3889) and 2,7-dibromophenanthrene-9,10-dione (THVo, M. Shekhirev, DA Kunkel, F. Orange, MJ-F. Guiner, A. Endersbe, A. Sinitskii, Chem. Commun. [Chemical Communications], 2014, 50, 4172) were prepared by selective bromination of phenanthrene-9,10-dione according to published literature methods.

[0131] Multicomponent condensation reactions of 1,2-dicarbonyl compounds, aromatic aldehydes, anilines, and small molecules that can donate nitrogen atoms (such as ammonium acetate) in suitable media are a common route to obtain highly substituted imidazoles and fused imidazoles (K. Skonieczny, D. D. Gryko, J. Org. Chem., 2015, 80, 5753; M. M. Heravil, M. Daraiel, V. Zadsirjan, Mol. Divers., 2015, 19, 577; D. Kumar, K. R. J. Thomas, J. Photochem. Photobiol. A: Chem., 2011, 218, 162). The synthesis of 6,9-dibromo-1,2-bis(4-(tert-butyl)phenyl)-1H-phenanthro[9,10-d]imidazole was achieved via a multicomponent condensation of 3,6-dibromophenanthroline-9,10-dione, 4-tert-butylbenzaldehyde, 4-tert-butylaniline, and ammonium acetate in acetic acid (WC. Chen, Y. Yuan, Y. Xiong, A. A. Rogach, QX. Tong, C. S. Lee, ACS Appl. Mater. Interfaces, 2017, 9, 26268). Using the same reaction conditions and reagents, 2,7-dibromophenanthroline-9,10-dione was converted to 5,10-dibromo-1,2-bis(4-(tert-butyl)phenyl)-1H-phenanthro[9,10-d]imidazole (Scheme 5).

[0132]

[0133] The multi-component condensation described in Scheme 1 was repeated, but starting with 3,6-dibromophenanthrene-9,10-dione, and 4-bromobenzaldehyde or pyridine-4-carboxaldehyde was used as the aldehyde component to obtain 6,9-dibromo-2-(4-bromophenyl)-1-(4-(tert-butyl)phenyl)-1H-phenanthro[9,10-d]imidazole or 6,9-dibromo-1-(4-(tert-butyl)phenyl)-2-(pyridin-4-yl)-1H-phenanthro[9,10-d]imidazole (Scheme 6).

[0134]

[0135] The aforementioned bromine-substituted imidazole and phenanthrene[9,10-d]imidazole are each subjected to a common Suzuki cross-coupling scheme with 4-(4,4,5,5-tetramethyl-1,3,2-dioxaborhecyclopentan-2-yl)pyridine in a mixed solvent system using a carbonate base and a palladium catalyst (typically tetra(triphenylphosphine)palladium(0)) to provide poly(4-pyridyl)-substituted imidazole and phenanthrene[9,10-d]imidazole (Scheme 7). Suzuki coupling of 4-(4,4,5,5-tetramethyl-1,3,2-dioxaborhecyclopentan-2-yl)pyridine with aryl bromides has been widely reported (M. Jurícek, JC Barnes, EJ Dale, WG. Liu, NL Strutt, CJ Bruns, NA Vermeulen, KC Hooray, AAS Arjeant, CLS Tern, YY Botros, WA Goddard, JFS Toddart, J. Am. Chem. Soc., 2013, 135, 12736; Y. Nakamura, N. Aratani, A. Osuka, Chem. Asian J., 2007, 2, 860; V. Gray, K. D. Dzebo, M. Abrahamsson, B. Albinsson, K. Moth-Poulsen, J. Phys. Chem. C, 2016, 120, 19018 (Scheme 7).

[0136]

[0137] Methyl toluenesulfonate has been used as an effective methylating agent, either in its pure form or with a co-solvent (JFS Carvalho, J. Louvel, MLJ Doornbos, E. Klaase, Z. Yu, J. Brussee, API Jzerman, J. Med. Chem. [Journal of Medicinal Chemistry], 2013, 56, 28-28; AN Woodward, J. M Kolesar, S. Sall, NA. Saleh, DS Jones, MG Walter, J. Am. Chem. Soc. [Journal of the American Chemical Society], 2017, 139, 846). 7; L. Pescatori, A. Arduini, A. Pochini, A. Secchi, C. Massera, F. Ugozzoli, Org. Biomol. Chem. [Organic and Biomolecular Chemistry], 2009, 7, 3698; M. Kuroboshi, T. Yamamoto, H. Tanaka, Synlett [Synthetic Letters], 2013, 24, 0197; JAZoltewicz, MPC Cruskie, Jr., Tetrahedron [Tetrahedron], 1995, 51, 3103). In this work, methyl toluenesulfonate was used to simultaneously N-methylate the N-atom of the pyridine ring and the N3 of the imidazole ring. The resulting poly(toluenesulfonate) salts were directly converted into their fluoroborates (Scheme 8).

[0138]

[0139] 2-(pyridin-4-yl)benzoselenazole was synthesized according to a modified literature method (T. Su, S. Xie, B. Li, J. Yan, L. Huang, X. Li, Synlett [Synthetic Express] 2015; 26, 215). The selective alkylation of the pyridine N-atom of 2-(pyridin-4-yl)benzoselenazole was accomplished by reaction with a suitable alkyl halide (Scheme 11). Alternatively, the pyridine N-atom arylation of 2-(pyridin-4-yl)benzoselenazole was performed using an aryl iodonium salt according to a generally accepted literature scheme (T. Lv, Z. Wang, J. You, J. Lan and G. Gao, J. Org. Chem., 2013, 73, 5723; C. Reus, M. Stolar, J. Vanderkley, J. Neubauer and T. Baumgartner, J. Am. Chem. Soc., 2015, 137, 11710). Finally, the counterion was exchanged with NaBF4 or NH4PF6 to obtain the target electrochromic compound (Scheme 9).

[0140]

[0141] Benzoxazole can be obtained via a similar route to that used to obtain benzothiazole. In the presence of air, the condensation of 2-aminophenol with pyridine-4-carboxaldehyde exclusively yields a 2,3-dihydrobenzoxazole derivative. The dehydrogenation of 2-(4-pyridyl)benzoxazole is then readily accomplished by treatment with 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ) in dichloromethane. Both N-alkylation and N-arylation of the pyridine moiety can be performed using standard methods (Scheme 10).

[0142]

[0143] Many methods can be used to construct other fused-ring azoles. For example, 2-arylnaphtho[1,2-d]thiazole can be obtained from a one-pot dehydrogenation (Semler-Wolf aromatization)-sulfur transfer-cyclization condensation sequence between 1-tetrahydronaphthone oxime O-acetate and an aromatic aldehyde in DMSO in the presence of elemental sulfur (Z. Xu, H. Huang, H. Chen and G.-J. Deng, Org. Chem. Front. [Organic Chemistry Frontiers], 2019, 6, 3060). In this manner, 2-(pyridin-4-yl)benzothiazole is obtained, and the pyridine moiety is selectively N-arylated by Cu catalysis using a common method. Subsequently, N-methylation of the thiazole ring is achieved by treatment with MeOTf. (Scheme 11) These quaternization reactions are widely applicable to other bicyclic systems.

[0144]

[0145] 3-aryl-1,2-benzisothiazoles, including 3-(pyridin-4-yl)-derived compounds, can be obtained by quenching anisole dianion with 4-pyridinecarboxynitrile (obtained by lithiation with BuLi-TMEDA in TBME) (R. Zhu, Z. Liu, J. Chen, X. Xiong, Y. Wang, L. Huang, J. Bai, Y. Deng and J. Huang, Org. Lett. [Organic Letters], 2018, 20, 3161) (Scheme 12)

[0146]

[0147] 3-(hetero)aryl-1,2-benzoisoxazole can be readily obtained by intramolecular cyclization of oxime or imine derived from 2-halobenzophenone or 2-hydroxybenzophenone (see F. Gualtieri and M. Gianniella, Isoxazoles, edited by P. Grünanger and P. Vita Finzi, Chemistry of Heterocyclic Compounds, John Wiley & Sons Inc., 1999, Vol. 48, Part 2, p. 1). According to the literature method (H. Hepburn and TJ Donohoe, Chem. Eur. J. [European Journal of Chemistry], 2020, 26, 1963), 3-(pyridin-4-yl)-1,2-benzisoxazole was prepared by oxidative cyclization of an imine derived from 4-(2-hydroxybenzoyl)pyridine with N-chlorosuccinimide (Scheme 13).

[0148]

[0149] Electrochromic Composition

[0150] The present invention also relates to electrochromic compositions comprising at least one compound of formula (I) as defined above as an oxidative electroluminescent compound. One or more additional oxidative electrochromic compounds may be added to the compositions of the present invention to suit the color or intensity of the colored state of the composition. The additional compound may be another compound of formula (I) or a different compound, such as a compatible dye or pigment. For example, the additional oxidative electrochromic compound may be selected from alkyl viologen, aryl viologen, alkylaryl viologen, or anthraquinones and their derivatives. Preferably, the additional compound has a redox potential close to that of the compound of formula (I).

[0151] The composition may further comprise at least one reducing compound. The reducing compound may also be an electrochromic compound. Examples of reducing compounds include 5,10-dihydrophenazine, phenothiazine, phenoxazine, N,N,N',N'-tetramethyl-p-phenylenediamine, thionethracene, tetrathionefulvalene, ferrocene, and their derivatives.

[0152] The compositions of the present invention may include a host medium, which may be a fluid, a mesocrystalline medium, or a gel. The host medium is introduced into the compositions of the present invention to dissolve the electrochromic compound. The host medium is preferably selected from the group consisting of organic solvents, liquid crystals, polymers, liquid crystal polymers, and mixtures thereof.

[0153] Examples of suitable organic solvents that can be used as the host medium are redox-compatible solvents that do not react with the electrochromic compound of the composition, such as ethylene carbonate, propylene carbonate, γ-butyrolactone, γ-valerolactone, acetonitrile, propionitrile, benzyl nitrile, glutaronitrile, methylglutaronitrile, dimethylformamide, N-methylpyrrolidone, sulfolane, 3-methylsulfolane, benzene, toluene, methyl ethyl ketone, acetone, ethanol, tetrahydrofurfuryl alcohol, 2-methoxyethyl ether, xylene, cyclohexane, 3-methylcyclohexanone, ethyl acetate, ethyl phenylacetate, tetrahydrofuran, methanol, methyl propionate, ethylene glycol, ethylene carbonate, ionic liquids, and mixtures thereof. Carbonates are preferred, and propylene carbonate is particularly important.

[0154] Suitable examples of liquid crystals that can be used as the host medium are nematic or chiral nematic media.

[0155] Examples of suitable polymers that can be used as the host medium are polymers that are solvent-soluble, particularly PMMA or other acrylate polymers, polyurethanes, polyethylene oxide, polypropylene oxide, polyvinyl acetate, poly(N-vinylpyrrolidone), and polyvinylidene fluoride.

[0156] Examples of suitable liquid crystal polymers that can be used as the host medium include Merck RM257, LC242, or SLM 90519. These liquid crystal polymers are typically used in combination with organic solvents, such as one of the organic solvents mentioned above.

[0157] Electrochromic device

[0158] The present invention also relates to an electrochromic device comprising a compound or composition having formula (I) according to the present invention. The device may be selected from optical articles, preferably optical lenses or filters, windows, preferably aircraft windows, goggles, mirrors, and displays, particularly segmented or matrix displays. Preferably, the device of the present invention is an optical article, more preferably an optical lens, and even more preferably an ophthalmic lens.

[0159] Non-limiting examples of ophthalmic lenses include corrective and uncorrective lenses, including monocular or multi-lens lenses, which may be segmented or non-segmented, and other elements for correcting, protecting, or enhancing vision, including but not limited to contact lenses, intraocular lenses, sunglasses, ski goggles, magnifying lenses, protective lenses, or goggles such as motorcycle goggles and helmets. Non-limiting examples of display elements and devices include screens and monitors. Non-limiting examples of windows include automotive, marine, and aircraft windows, filters, shaders, and optical switches.

[0160] Preferably, the apparatus of the present invention includes a mechanism for maintaining the compound or composition of the present invention in a mechanically stable environment. More preferably, the apparatus may include a pair of opposing substrates having a gap therebetween for receiving a mixture of the main medium of the present invention and the compound or composition, and a frame for maintaining the substrates adjacent to each other.

[0161] The device of the present invention may therefore include an optical component equipped with at least one transparent unit arranged side by side in a direction parallel to its surface, as disclosed in WO 2006 / 013250, each unit being tightly closed and containing at least one compound or composition of the present invention.

[0162] Other devices according to the invention may be devices comprising at least one compound or composition of the invention, as described in FR 2937154 or FR 2950710.

[0163] Example

[0164] The present invention will be further illustrated by the following non-limiting examples, which are given for illustrative purposes only and should not limit the scope of the appended claims.

[0165] Synthesis of the compounds of the present invention

[0166] 1. (iso)thiazol benzoxone compounds

[0167] Example 1

[0168] 2-(pyridin-4-yl)benzothiazole

[0169]

[0170] A solution of 2-aminothiophenol (7.01 g, 56.1 mmol) and pyridine-4-carboxaldehyde (6.00 g, 56.1 mmol) in EtOH (28 mL) was stirred under air for 120 hours. The resulting mixture was filtered, and the residue was washed with cold MeOH (20 mL) and air-dried to give the title compound (7.63 g, 64%) as a creamy powder. The liquid volume was reduced and filtered to give a second batch of product (0.73 g, 6%), δ H (CDCl3, 400MHz) 7.46 (1H, dt, J = 1.2 and 8.2Hz), 7.56 (1H, dt, J = 1.2 and 8.2Hz), 7.93–7.99 (3H, m), 8.14 (1H, ddd, J = 8.2Hz) and 8.78 (2H, dd, 1.6 and J = 4.5Hz); δ C(CDCl3, 100MHz) 121.21, 121.89, 123.93, 126.22, 126.84, 135.21, 140.47, 150.79, 153.97 and 165.11.

[0171] 4-(benzothiazo-2-yl)-1-hexylpyridine-1-onium iodide

[0172]

[0173] A solution of 2-(pyridin-4-yl)benzothiazole (0.54 g, 2.5 mmol) and 1-iodohexane (1.62 g, 7.6 mmol) in MeCN (40 mL) was heated under reflux in the dark at N2 for 24 hours, then cooled and diluted with Et2O (50 mL). The precipitate was filtered off, washed with Et2O (3 × 20 mL), and air-dried to give the title compound (0.77 g, 71%) as a yellow powder. H (DMSO-d6, 400MHz) 0.85 (3H,t,J=7.0Hz), 1.21-1.37 (6H,m), 1.88-2.01 (2H,m), 4.65 (2H,t,J=7.3Hz), 7.62-7.72 (2H,m), 8.25 (1H,dd,J=0.9 and 7.6Hz), 8.35 (1H,dd,J=1.1 and 7.6Hz), 8.76 (2H,d,6.8Hz) and 9.23 (2H,d,J=6.8Hz); δ C (DMSO-d6, 100MHz) 14.32, 22.34, 25.54, 31.06, 31.19, 61.11, 123.72, 124.82, 125.47, 128.23, 128.33, 136.64, 146.29, 146.73, 153.83 and 161.90.

[0174] 4-(benzothiazo-2-yl)-1-hexylpyridine-1-onium tetrafluoroborate

[0175]

[0176] A solution of 4-(benzothiazol-2-yl)-1-hexylpyridin-1-onium iodide (0.77 g, 1.8 mol) in MeOH / H₂O (40 mL, 1:1) was added dropwise to a solution of NaBF₄ (3.96 g, 36 mmol) in water (80 mL) with stirring. Stirring was continued for 0.5 hours, and the resulting precipitate was filtered, washed with water (2 × 5 mL), and air-dried to give the title compound (0.69 g, 98%) as a pale yellow powder. H(DMSO-d6, 400MHz) 0.88 (3H,t,J=6.9Hz), 1.25-1.39 (6H,m), 1.89-2.02 (2H,m), 4.67 (2H,t,J=7.4Hz), 7.64-7.75 (2H,m), 8.28 (1H,dd,J=1 and 8.3Hz), 8.37 (1H,dd,J=1 and 7.6Hz), 8.79 (2H,d,6.8Hz) and 9.23 (2H,d,J=6.8Hz); δ C (DMSO-d6, 100MHz) 13.75, 21.78, 24.98, 30.50, 30.63, 60.57, 123.14, 124.26, 124.90, 127.67, 127.77, 136.09, 145.72, 146.19, 153.27 and 161.33.

[0177] Compound 1 2-(1-Hexylpyridin-1-onthiol-4-yl)-3-methylbenzothiazole-3-onthiol bis(tetrafluoroborate)

[0178]

[0179] A mixture of 4-(benzothiazol-2-yl)-1-hexylpyridin-1-onium tetrafluoroborate (0.59 g, 1.5 mmol) in MeOTs (1.71 g) was heated at 180 °C for 2 hours, cooled, ground with Et₂O (3 × 40 mL), and dried under N₂ to give 0.81 g of a light brown powder. The solid was redissolved in MeOTs (1.71 g), heated at 180 °C for 1 hour, cooled, ground again with Et₂O (4 × 30 mL), and air-dried. The colloidal solid was dissolved in MeOH / water (25 mL, 1:4) and added dropwise to a solution of NaBF₄ (3.38 g, 30.7 mmol) in water (50 mL) with stirring. Stirring was continued for 0.5 hours, and the resulting precipitate was filtered, washed with water (2 × 5 mL), air-dried, and ground with hot MeOH (8 mL). The residue was cooled, filtered, and washed with cold MeOH (2 mL) to give the title compound (0.38 g, 51%) as a creamy powder, δ H[(CD3)2CO,400MHz]0.91(3H,t,J=7.0Hz),1.29-1.47(4H,m),1.49-1.61(2H,m),2.20-2.32(2H,m),4.58(3H,s),5.04(2H,t,J=7.7Hz),8 .07(1H,t,J=7.9Hz), 8.17(1H,t,J=7.8Hz), 8.58(1H,d,J=8.4Hz), 8.68(1H,d,J=8.4Hz), 8.89(2H,bd,J=5.7Hz) and 9.59(2H,d,J=6.5Hz); δ F [(CD3)2CO,376MHz]-151.40,-151.35; δ C [(CD3)2CO,100MHz]13.30,22.14,25.54,30.98,31.37,38.42,62.91,117.97,124.70,129.92,130.08,131.05,131.42,141.05,142.81,146.47 and 168.29.

[0180] Example 2

[0181] 4-(benzothiazo-2-yl)-1-phenylpyridine-1-onium trifluoromethanesulfonate

[0182]

[0183] A mixture of 2-(pyridin-4-yl)benzothiazole (1.34 g, 6.3 mmol), diphenyliodonium trifluoromethanesulfonate (3.47 g, 8.1 mmol), and Cu(OAc)₂·H₂O (0.11 g, 0.55 mmol, 10 mol%) in anhydrous DMF (25 mL) was heated at 100 °C for 16 hours, cooled, and the solvent was removed under reduced pressure. The residue was ground with Et₂O (3 × 40 mL) and air-dried to give the title compound (2.66 g, 96%) as a yellow powder. H [(CD3)2CO,400MHz]7.67-7.86(5H,m),8.01-8.09(2H,m),8.27-8.37(2H,m),9.02(2H,d,6.8Hz) and 9.56(2H,d,J=6.8Hz); δ F [(CD3)2CO, 376MHz] -77.76; δ C(DMSO-d6, 100MHz) 122.93, 124.60, 124.85, 125.25, 128.01, 128.18, 130.60, 131.78, 136.92, 142.95, 142.95, 145.92, 148.33, 154.18 and 160.76.

[0184] Compound 2: 3-Methyl-2-(1-phenylpyridin-1-onthiol-4-yl)benzothiazolyl-3-onthiol bis(tetrafluoroborate)

[0185]

[0186] A mixture of 4-(benzothiazol-2-yl)-1-phenylpyridin-1-onium trifluoromethanesulfonate (1.07 g, 2.4 mmol) and MeOTs (3.62 g, 19 mmol) was heated at 180 °C for 3 hours, cooled, and ground with Et₂O (3 × 40 mL). The residue was then dried under vacuum. The residue was dissolved in MeOH (5 mL) and added dropwise with stirring to a solution of NaBF₄ (5.37 g, 48.8 mmol) in water (40 mL). Stirring was continued for 0.5 hours, and the resulting precipitate was filtered, washed with water (2 × 5 mL), and air-dried. The residue was ground with hot MeOH (2 × 20 mL), filtered, and air-dried to give the title compound (0.72 g, 62%) as a gray powder. H (DMSO-d6,400MHz)4.32(3H,s),7.80-7.90(3H,m),7.92-7.99(2H,m),8.04(1H,t,J=7.8Hz),8.14(1H, t,J=7.5Hz), 8.55(1H,d,J=8.6Hz), 8.69(1H,d,J=8.2), 8.79(2H,d,J=6.7Hz) and 9.77(2H,d,J=6.7Hz); δ F (DMSO-d6,376MHz)-148.23,-148.18; δ C (DMSO-d6, 100MHz) 118.42, 125.21, 125.57, 129.92, 130.10, 130.99, 131.21, 131.61, 132.40, 141.77, 142.47, 142.92, 146.55 and 168.49.

[0187] Example 3

[0188] (E)-3,4-dihydronaphthyl-1(2H)-oneO-acetyloxime

[0189]

[0190] Solid hydroxylamine hydrochloride (7.14 g, 103 mmol) was added in a single step to a solution of 3,4-dihydronaphthyl-1(2H)-one (10.00 g, 68.5 mmol) in EtOH (30 mL). The resulting solution was heated at 60 °C for 1 hour, poured into HCl (200 mL, 2 M), and extracted with EtOAc (3 × 50 mL). The combined organic extracts were washed with brine (50 mL), then washed with water (50 mL), dried (Na₂SO₄), and the solvent was removed under reduced pressure. The residue was dissolved in pyridine (32 mL), and then Ac₂O (13.97 g, 137 mmol) and DMAP (16 mg) were added. The resulting solution was stirred at room temperature for 1 hour, poured into HCl (300 mL, 2 M), and extracted with EtOAc (3 × 200 mL). After drying (Na₂SO₄), the solvent was removed under reduced pressure. The residue was crystallized twice from EtOAc / hexane to give the title compound (10.51 g, 76%) as colorless needles, δ H (CDCl3, 400MHz) 1.87–1.93 (2H, m), 2.27 (3H, s), 2.77–2.82 (2H, br.t, J = 6.1 Hz), 2.86–2.90 (2H, m), 7.16–7.20 (1H, m), 7.22–7.26 (1H, m), 7.34 (1H, dt, J = 1.4 and 7.4 Hz) and 8.13–8.16 (1H, m); δ C (CDCl3, 100MHz) 19.92, 21.33, 25.60, 29.55, 125.61, 126.59, 128.72, 128.95, 130.74, 140.93, 161.31 and 169.22.

[0191] 2-(pyridin-4-yl)naphtho[1,2-d]thiazole

[0192]

[0193] A mixture of (E)-3,4-dihydronaphthyl-1(2H)-one O-acetyl oxime (4.00 g, 19.7 mmol), pyridine-4-carboxaldehyde (1.40 g, 13.1 mmol), and sulfur (10.09 g, 39.4 mmol) in DMSO (60 mL) was heated at 120 °C for 4 hours under N2, poured into water (200 mL), and extracted with EtOAc (3 × 100 mL). The combined extracts were washed with water (100 mL), dried (Na2SO4), and the solvent was removed under reduced pressure. The residue was chromatographically separated on silica using EtOAc (25%–30%, in a hexane gradient) as the eluent. Fluorescent bands were collected, and the solvent was removed under reduced pressure. The residue was crystallized from hot EtOAc / hexane at 0 °C to give the title compound (1.14 g, 33%) as brown needles, δ H (CDCl3, 600MHz) 7.64 (1H, ddd, J = 1.3, 6.9 and 8.1Hz), 7.74 (1H, ddd, J = 1.2, 6.9 and 8.2Hz), 7.87-7.90 (1H, br.dm, J = 8.7Hz), 7.95 (1H, d, J = 8.7Hz), 7.98-8.01 (1H, br.m, J = 8.1Hz), 8.06 (2H, d, J = 6.0Hz), 7.80 (2H, d, J = 6.0Hz) and 8.93 (1H, br.d, J = 8.2Hz); δ C (CDCl3, 125MHz) 118.90, 120.98, 123.96, 126.61, 127.17, 127.40, 128.22, 128.92, 132.16, 132.33, 140.77, 150.56, 150.78 and 163.88.

[0194] 4-(naphtho[1,2-d]thiazolyl-2-yl)-1-phenylpyridine-1-onium trifluoromethane sulfonate

[0195]

[0196] A mixture of 2-(pyridin-4-yl)naphtho[1,2-d]thiazole (1.12 g, 4.3 mmol), diphenyliodonium trifluoromethane sulfonate (2.20 g, 5.1 mmol), and Cu(OAc)₂·H₂O (86 mg, 10 mol%) in DMF (30 mL) was heated at 100 °C for 16 hours under N₂. The resulting solution was cooled and the solvent was removed under reduced pressure. The residue was ground with Et₂O (3 × 30 mL) and air-dried to give the title compound (2.09 g, 100%) as a brown powder, which was used in the next step without further purification. H(DMSO-d6,400MHz)7.71-7.91(5H,m),7.93-8.01(2H,m),8.16-8.23(2H,m),8.40(1 δ F (DMSO-d6, 376MHz) -77.75.

[0197] Compound 3: 1-Methyl-2-(1-phenylpyridin-1-onthien-4-yl)naphtho[1,2-d]thiazolyl-1-onthienylbis(tetrafluoroborate)

[0198]

[0199] A solution of 4-(naphtho[1,2-d]thiazolyl-2-yl)-1-phenylpyridin-1-onium trifluoromethanesulfonate (2.09 g, 4.3 mmol) in methyl trifluoromethanesulfonate (9.03 g, 55.1 mmol) was heated under reflux. After 2 days, the solution was diluted with Et2O (40 mL), and the residue was collected by filtration. The filtrate was washed with Et2O (2 × 10 mL) and air-dried. The solid was extracted with water (2 × 100 mL) and the solvent was removed under reduced pressure. The residue was then dissolved in MeOH (5 mL) and added dropwise with stirring to a solution of NaBF4 (5.05 g, 45.9 mmol) in water (40 mL). Stirring was continued for 0.5 h, and the resulting precipitate was filtered, washed with water (3 × 5 mL), and ground with hot MeOH (20 mL). After cooling, the residue was filtered off and air-dried to give the title compound (0.23 g, 8%) as a pale yellow solid. δ H (DMSO-d6,400MHz)4.74(3H,s),7.76-8.12(7H,m),8.40-8.70(3H,br.m),8. 82 (2H, br.d, J = 3.3Hz), 9.11 (1H, d.dm, J = 9.0Hz) and 9.79 (2H, br.d, J = 3.3Hz); δ F (DMSO-d6, 376MHz) -148.25 and -148.20.

[0200] Example 4

[0201] Quinoline-4-carboxaldehyde

[0202]

[0203] A mixture of 4-methylquinoline (6.00 g, 41.9 mmol), p-toluenesulfonic acid (7.22 g, 42 mmol), and iodine (4.26 g, 16.8 mmol, 40 mol%) in DMSO (300 mL) was heated at 130 °C for 16 h, cooled, poured into water (400 mL), and alkalized (K₂CO₃). The mixture was extracted with EtOAc (5 × 100 mL). The combined organic extracts were washed with an aqueous solution of Na₂S₂O₃ (300 mL), then washed with brine (200 mL), and dried (Na₂SO₄). The solvent was removed under reduced pressure to give the title compound (6.11 g, 93%) as a beige solid, δ H (CDCl3, 400MHz) 7.75 (1H, ddd, J = 1.4, 6.9 and 8.4Hz), 7.80 (1H, d, J = 4.3Hz), 7.83 (1H, d, J = 1.4, 6.9 and 8.4), 8.23 ​​(1H, ddd, J = 0.7, 1.4 and 8.4Hz), 9.11 (1H, ddd, J = 0.7, 1.4 and 8.4Hz), 9.21 (1H, d, J = 4.3Hz) and 10.53 (1H, s); δ C (CDCl3, 100MHz) 123.89, 124.44, 125.87, 129.42, 130.06, 130.22, 136.76, 149.28, 150.48 and 192.92.

[0204] 2-(quinolin-4-yl)-2,3-dihydrobenzothiazole

[0205]

[0206] A solution of quinoline-4-carboxaldehyde (3.00 g, 19.1 mmol) and 2-aminobenzylthiophenol (2.39 g, 19.1 mmol) in EtOH (40 mL) was stirred under air for 2 days. The solvent was decanted, and the residue was crystallized from hot EtOH (40 mL) and cooled to 0 °C. The product was collected by filtration, washed with EtOH (10 mL), and air-dried to give the title compound (2.38 g, 47%) as an orange prismatic compound. The filtrate was reduced to give a second batch of product (1.19 g, 23%) as a yellow powder. H(DMSO-d6, 400MHz) 6.62 (1H, dt, J = 1.2 and 7.5Hz), 6.78 (1H, br.dd, J = 1.1 and 7.8Hz), 6.94 (1H, dt, J = 1.3 and 7.7Hz), 6.99 (1H, dd, J = 1.2 and 7.4Hz), 7.15 (2H, s), 7.62 (1H, d, J = 4.5Hz), 7.67 (1H, ddd, J = 1.4, 6.9 and 8.4Hz), 7.79 (1H, ddd, J = 1.4, 6.9, 8.4Hz), 8.07 (2H, br.t, J = 8.8Hz), and 8.88 (1H, d, J = 4.4Hz); δ C (DMSO-d6, 100MHz) 64.46, 109.88, 117.60, 119.59, 121.94, 123.84, 124.74, 125.14, 126.21, 127.39, 129.94, 130.26, 148.02, 148.16, 148.40 and 151.08.

[0207] 2-(quinolin-4-yl)benzothiazole

[0208]

[0209] Solid DDQ (1.29 g, 5.7 mmol) was added to a solution of 2-(quinolin-4-yl)-2,3-dihydrobenzothiazole (1.50 g, 5.7 mmol) in DCM (1.2 L). The mixture was stirred at room temperature for 1 hour and then filtered through silica using EtOAc (60%, in hexane) as the eluent. The solvent was removed under reduced pressure, and the residue was dissolved in EtOAc (200 mL) and washed successively with KOH (200 mL, 2 M), water (2 × 100 mL), and brine (100 mL). The extract was dried (Na₂SO₄) and the solvent was removed under reduced pressure. The residue was crystallized from hot EtOAc / hexane. After cooling to -4 °C, the product was collected by vacuum filtration and washed with cold hexane to give the title compound (1.19 g, 80%) as a pale lime needle, δ H(CDCl3, 400MHz) 7.52 (1H, ddd, J = 1.3, 7.3 and 7.9Hz), 7.60 (1H, ddd, J = 1.3, 7.2 and 8.2Hz), 7.70 (1H, ddd, J = 1.3, 6.8 and 8.7Hz), 7.80 (1H, d, J = 4.4Hz), 7.82 (1H, ddd, J = 1.4, 6.9 and... 8.4Hz), 8.02 (1H, ddd, J = 0.7, 1.3 and 8.0Hz), 8.22 (1H, ddd, J = 0.7, 1.4 and 8.4Hz), 8.24 (1H, ddd, J = 0.6, 1.2 and 8.2Hz), 9.00 (1H, ddd, J = 0.7, 1.4 and 8.5Hz) and 9.05 (1H, d, J = 4.4Hz); δ C (CDCl3,100MHz)121.63,122.19,124.12,124.98,126.04,126.17,126.76 ,128.19,130.00(2×C),135.34,138.32,149.20,149.80,154.18,164.80.

[0210] 4-(benzothiazol-2-yl)-1-phenylquinoline-1-onium tetrafluoroborate

[0211]

[0212] A mixture of 2-(quinolin-4-yl)benzothiazole (1.00 g, 3.8 mmol), diphenyliodonium trifluoromethanesulfonate (2.46 g, 5.7 mmol), and Cu(OAc)₂·H₂O (76 mg, 10 mol%) in DMF (30 mL) was heated at 100 °C for 16 hours under N₂. The resulting solution was cooled and the solvent was removed under reduced pressure. The residue was ground with Et₂O (3 × 40 mL) to give a mixture of product and starting material (62:38). The residue in DMF (30 mL) and diphenyliodonium trifluoromethanesulfonate (1.64 g, 3.8 mmol) and Cu(OAc)₂·H₂O (76 mg, 10 mol%) were heated at 100 °C for 16 hours under N₂. The resulting solution was cooled and the solvent was removed under reduced pressure. The residue was ground with Et₂O (3 × 40 mL) to give a mixture of product and reactants (70:30). This solid was dissolved in warm MeOH (20 mL) and added dropwise to a solution of NaBF₄ (8.40 g, 76 mmol) in water (50 mL) with stirring. Stirring was continued for 0.5 hours, and the resulting precipitate was collected by filtration and washed with water (5 mL). The solid was dissolved in hot MeOH (20 mL) and added dropwise to a solution of NaBF₄ (8.40 g, 76 mmol) in water (50 mL) with stirring. Stirring was continued for 0.5 hours, and the resulting precipitate was filtered, washed with water (5 mL), and air-dried to give a yellow powder. The powder was ground with hot EtOH (2 × 5 mL) to give the title compound (1.01 g, 54%) as a yellow powder, δ H (CDCl3,400MHz)7.67-7.79(2H,m),7.79-8.92(6H,m),8.12-8.24(2H,m),8.27(1H,br.d,J=7.6Hz),8. 38 (1H, br.d, J = 7.9Hz), 8.68 (1H, d, J = 6.2Hz), 9.52 (1H, d, J = 6.2Hz) and 9.69 (1H, br.dd, J = 1.5 and 8.3Hz); δ F (CDCl3, 376MHz) -154.67 and -154.62; δ C (CDCl3, 100MHz) 120.31, 122.03, 122.56, 124.59, 126.34, 126.89, 127.61, 127.76, 128.91, 130.47, 131.13, 131.79, 135.76, 136.23, 140.35, 140.92, 148.20, 149.02, 154.37 and 161.44.

[0213] Compound 4:3-Methyl-2-(1-phenylquinoline-1-onthiol-4-yl)benzothiazol-3-onthiol tetrafluoroborate

[0214]

[0215] A mixture of 4-(benzothiazol-2-yl)-1-phenylquinoline-1-onium tetrafluoroborate (1.01 g, 2.4 mmol) in MeOTs (4.61 g, 24.8 mmol) was heated at 180 °C for 3 hours, then cooled and ground with Et2O (3 × 30 mL). The washings were discarded, and the residue was then dried under N2. The residue was dissolved in hot MeOH (40 mL) and added dropwise with stirring to a solution of NaBF4 (4.55 g, 41.4 mmol) in water (40 mL). Stirring was continued for 0.5 hours, and the precipitate was collected by filtration and washed with water (2 × 5 mL), then washed with hot MeOH (5 mL) and air-dried. The residue was ground with AcMe (3 mL) to give the title compound (0.70 g, 56%) as a grayish-white powder, δ H [(CD3)2CO, 600MHz] 4.52 (3H, s), 7.88–8.02 (5H, m), 8.07 (1H, app.br.d, J = 9.0Hz), 8.12 (1H, ddd, J = 0.7, 7.3, and 8.7Hz), 8.19–8.24 (2H, m), 8.39 (1H, ddd, J = 1.3, 7.0, and 9.0Hz), 8.57 (1H, ddd, J = 0.6, 1.3, and 8.5Hz), 8.64 (1H, ddd, J = 0.7, 1.6, and 7.9Hz), 8.75 (1H, ddd, J = 0.6, 1.2, and 7.3Hz), 9.00 (1H, d, J = 5.9Hz) and 9.97 (1H, d, J = 5.9Hz); δ F [(CD3)2CO,470MHz]-151.44 and -151.39; δ C [(CD3)2CO,125MHz]38.76,118.09,121.40,124.76,125.84,126.59,127.07,128.87,130.00,130.73,131.06,132.25,132.32,132.52,137.16,140.39,140.69,141.56,142.98,150.58 and 166.95.

[0216] Example 5

[0217] 3-(pyridin-4-yl)-1,2-benzisothiazole

[0218]

[0219] Under N2, n BuLi (2.5 M, in hexane) (32.2 mL, 80.5 mmol) was added dropwise to a stirred solution of anisole (2.00 g, 16.1 mmol) and N,N,N',N'-tetramethylethylenediamine (5.60 g, 7.24 mL, 48.3 mmol) in tert-butyl methyl ether (80 mL). The reaction mixture was then stirred at room temperature under N2 for 3 h. 4-pyridinecarboxynitrile (16.76 g, 161 mmol) was then added in portions, and the reaction mixture was stirred at room temperature under N2 for 24 h. The reaction mixture was then carefully quenched with saturated NH4Cl aqueous solution (100 mL) and extracted with DCM (3 × 200 mL). The organic layers were combined, dried (Na2SO4), filtered, and the solvent was removed under reduced pressure. The resulting residue was subjected to chromatographic separation on silica gel [eluent = 1:9, increasing to 4:6 EtOAc:DCM]. The solvent in the resulting column fraction was removed under reduced pressure, and the residue was further separated chromatographically on silica gel [eluent = 1:9, increasing to 4:6 EtOAc:DCM]. The solvent in the resulting column fraction was removed under reduced pressure, and the residue was recrystallized from hot petroleum ether and filtered to give the title compound (0.33 g, 15%) as colorless crystals. The filtrate from the recrystallization was allowed to stand at -20°C for 16 hours to give a second batch of product (0.15 g, 7%) as colorless crystals. Yield: 0.48 g, 22%. δ H (CDCl3,400MHz)8.81(2H,d,J=5.3Hz),8.18(1H,d,J=8.2Hz),8.02(1H,d,J= 8.2Hz), 7.79(2H,d,J=5.9Hz), 7.59(1H,t,J=7.3Hz) and 7.50(1H,t,J=7.3Hz); δ C (CDCl3, 100MHz) 161.4, 153.9, 150.5, 142.2, 133.36, 127.9, 125.6, 124.1, 123.0 and 120.2.

[0220] Compound 5 4-(1,2-Benzisothiazo-3-yl)-1-phenylpyridine-1-onium tetrafluoroborate

[0221]

[0222] 3-(pyridin-4-yl)-1,2-benzisothiazole (0.36 g, 1.7 mmol), diphenyliodonium trifluoromethanesulfonate (1.12 g, 2.6 mmol), and Cu(OAc)₂·H₂O (34 mg, 0.17 mmol) were dissolved in DMF (20 mL) under N₂, and the reaction mixture was stirred at 100 °C for 16 hours. The reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. The resulting pale yellow solid was ground with diethyl ether (3 × 50 mL), filtered, and dried under reduced pressure. The resulting pale yellow solid was dissolved in hot MeOH (150 mL) and added dropwise through a cotton plug to a stirred solution of NaBF₄ (15.0 g) in H₂O (300 mL), thereby forming a pale yellow precipitate. The suspension was stirred for 30 minutes and then filtered under reduced pressure. The resulting solid was washed with water (30 mL) and then dried under reduced pressure to give a pale yellow powder. The solid was then dissolved in hot acetone and added dropwise through a cotton plug back into the filtrate (which had been reduced by about 30% under vacuum), yielding a pale yellow precipitate. The resulting suspension was filtered under reduced pressure, and the solid thus obtained was washed with water (30 mL) and then dried under reduced pressure to give the title compound as a pale yellow powder. Yield: 0.38 g, 59%. δ H δ C (DMSO-d6, 100MHz) 157.4, 154.0, 148.8, 145.6, 142.5, 132.8, 131.4, 130.3, 128.6, 126.8, 126.6, 124.8, 123.9 and 121.5; δ F (DMSO-d6,376MHz)-148.22(4F,br.m).

[0223] Example 6

[0224] Compound 6: 2-Methyl-3-(1-phenylpyridin-1-onthiol-4-yl)-1,2-benzisothiazol-2-onthiol bis(hexafluorophosphate)

[0225]

[0226] 4-(1,2-benzisothiazol-3-yl)-1-phenylpyridin-1-onium tetrafluoroborate (0.30 g, 0.8 mmol) was suspended in methyl trifluoromethanesulfonate (0.8 g, 5.4 mmol), and the reaction mixture was stirred at 100 °C for 80 min under N2. The reaction mixture was then stirred at 40 °C for 4 h under N2. After cooling to room temperature, ether (50 mL) was added, and the resulting suspension was filtered to obtain a brown powder, which was then ground with ether (3 × 50 mL) and dried under reduced pressure. This brown powder was then dissolved in hot MeOH (50 mL) and added dropwise through a cotton plug to a stirred solution of NH4PF6 (10.0 g) in H2O (200 mL), thereby forming a brown precipitate. The precipitate was then washed with water (30 mL) and dried under reduced pressure to obtain a light brown powder. The light brown powder was then recrystallized from hot MeOH to give the title compound as a light brown powder, in a yield of 0.18 g (38%). H (DMSO-d6,400MHz)9.81(2H,d,J=6.9Hz),8.75(2H,d,J=6.9Hz),8.71(1H,d,J=6.6Hz),8 .18(1H,ddd,J=8.5,7.3,0.9Hz), 8.10(1H,d,J=6.6Hz), 8.05-7.82(6H,m) and 4.33(3H,s); δ C (DMSO-d6, 100MHz) 159.3, 147.8, 146.2, 142.5, 142.4, 134.5, 131.9, 130.9, 130.5, 129.3, 128.8, 127.0, 124.7, 122.9 and 39.5; δ F (DMSO-d6,376MHz)-70.14(12F,d,J=711.5Hz).

[0227] 2. (benzo)imidazolium and fused-ring derivatives

[0228] Example 7

[0229] 2-(pyridin-4-yl)-1H-benzimidazole

[0230]

[0231] A solution of o-phenylenediamine (10.10 g, 93.5 mmol) and pyridine-4-carboxaldehyde (10.00 g, 93.5 mmol) in EtOH (500 mL) was stirred in air for 72 hours, and the solvent was removed under reduced pressure. The residue was crystallized from EtOAc / hexane and then ground three times with hot EtOAc to give the title compound (11.44 g, 63%) as a brown powder. H (DMSO-d6, 400MHz) 7.26 (2H, bs), 7.59 (1H, vbs), 7.71 (1H, vbs), 8.80 (2H, d, J = 6.1 Hz), 8.75 (2H, d, J = 6.1 Hz) and 13.26 (1H, bs).

[0232] 1-Methyl-2-(pyridin-4-yl)-1H-benzimidazole

[0233]

[0234] A mixture of 2-(pyridin-4-yl)-1H-benzimidazole (5.33 g, 27.3 mmol), MeI (5.33 mL, 12.15 g, 85.6 mmol), and KOH (7.83 g, 140 mmol) in acetone (660 mL) was stirred at room temperature for 2 hours and then poured into PhMe (700 mL). The resulting solution was washed with water (1 L) and brine (100 mL), dried (Na2SO4), and the solvent was removed under reduced pressure. The residue was filtered through neutral alumina using EtOAc as the eluent. The solvent was removed under reduced pressure, and the residue was crystallized from EtOAc / hexane to give the title compound (2.80 g, 49%) as a yellow plate, δ H (CDCl3, 400MHz) 3.83 (3H,s), 7.72–7.46 (3H,m), 7.72 (2H,d,J=6.0Hz), 7.83–7.87 (1H,m) and 8.06 (2H,d,J=6.0Hz); δ C (CDCl3, 100MHz) 31.84, 109.88, 120.37, 123.03, 123.45, 123.74, 136.74, 137.86, 142.91, 150.38 and 150.76.

[0235] 1-Hexyl-4-(1-methyl-1H-benzimidazol-2-yl)pyridine-1-onium tetrafluoroborate

[0236]

[0237] A solution of 1-methyl-2-(pyridin-4-yl)-1H-benzimidazole (1.47 g, 7 mmol) and 1-iodohexane (4.47 g, 21.1 mmol) in MeCN (40 mL) was heated under stirring in the dark at N2 under reflux. After 24 hours, the resulting mixture was cooled, diluted with Et2O (60 mL), filtered, washed with Et2O (30 mL), and dried under vacuum. The hygroscopic orange powder was dissolved in MeOH (30 mL) and added dropwise to a solution of NaBF4 (4.55 g, 41.4 mmol) in water (200 mL) with stirring. Stirring was continued for 0.5 hours, and the resulting precipitate was filtered, washed with water (3 × 10 mL), and air-dried to give the title compound (1.91 g, 73%) as a pale yellow powder. H [(CD3)2CO, 400MHz] 0.88 (3H,t,J=7.3Hz), 1.27-1.56 (6H,m), 2.15-2.27 (2H,m), 4.23 (3H,s), 4.93 (2H,t,J=7.7Hz), 7.39 (1H,ddd,J=1.1, 7.1 and 8.2Hz), 7.48 (1H,ddd,J=1.2, 7.1 and 8.2Hz), 7.70-7.74 (1H,m), 7.80-7.84 (1H,m), 8.80 (2H,d,J=6.9Hz) and 9.34 (2H,d,J=6.9Hz); δ F [(CD3)2CO, 376MHz] -151.70 and -151.54; δ C [(CD3)2CO,100MHz]13.31,22.17,25.54,31.00,31.24,32.08,61.60,111.15,120.61,123.44,125.00,127.04,137.95,143.21,145.02,145.87 and 147.05.

[0238] Compound 7: 2-(1-Hexylpyridin-1-onthien-4-yl)-1,3-dimethyl-1H-benzimidazole-3-onthienium bis(tetrafluoroborate)

[0239]

[0240] A mixture of 1-hexyl-4-(1-methyl-1H-benzimidazol-2-yl)pyridin-1-onthium tetrafluoroborate (0.50 g, 1.3 mmol) in MeOTs (4.00 g, 21.5 mmol) was heated at 180 °C for 90 min, cooled, and then ground with Et2O (3 × 30 mL). The residue was dissolved in MeOH (20 mL) and added dropwise with stirring to a solution of NaBF4 (20.97 g, 190 mmol) in water (100 mL). Stirring was continued for 0.5 h, and the resulting precipitate was filtered, washed with water (2 × 3 mL), and air-dried to give 2-(1-hexylpyridin-1-onthium-4-yl)-1,3-dimethyl-1H-benzimidazol-3-onthium bis(tetrafluoroborate) (0.45 g, 71%) as a gray powder. H (CD3OD,400MHz)0.91-0.99(3H,m),1.35-1.59(6H,m),2.10-2.22(2H,m),4.07(6H,s),4.81(2H, t,J=7.6Hz), 7.81-7.88(2H,m), 8.05-8.12(2H,m), 8.61(2H,d,J=5.4Hz) and 9.43(2H,d,J=5.4Hz); δ F (DMSO-d6, 376MHz) -148.25; δ C (DMSO-d6, 100MHz) 14.34, 22.34, 25.60, 31.14, 31.37, 33.44, 62.15, 114.19, 128.06, 130.84, 132.49, 136.91, 145.57 and 146.60.

[0241] Example 8

[0242] Compound 8 2-(1-Hexylpyridin-1-onthien-4-yl)-1,3-dimethyl-1H-benzimidazole-3-onthienium bis(hexafluorophosphate)

[0243]

[0244] Solid ammonium hexafluorophosphate (1.16 g, 7.1 mmol) was added to the aqueous filtrate and washings obtained during the preparation of compound 3 above, and the resulting precipitate was filtered, washed with water (2 × 2 mL), ground with hot MeOH (2 mL), and air-dried to give 2-(1-hexylpyridin-1-onthiol-4-yl)-1,3-dimethyl-1H-benzimidazole-3-onthiol bis(hexafluorophosphate) (0.21 g, 27%) as a creamy powder; δ H(DMSO-d6,400MHz)0.89(3H,t,J=6.8Hz),1.25-1.47(6H,m),1.94-2.08(2H,m),3.97(6H,s),4. 74(2H,m),7.81-7.88(2H,m),8.15-8.23(2H,m),8.63(2H,d,J=6.4Hz) and 9.48(2H,d,J=6.4Hz); δ F (DMSO-d6,376MHz)-70.13(d,J=710Hz); δ C (DMSO-d6, 100MHz) 14.34, 22.35, 25.60, 31.14, 31.40, 33.47, 62.14, 114.20, 128.09, 130.87, 132.48, 136.90, 145.57 and 146.61.

[0245] Example 9

[0246] 1-Hexyl-2-(pyridin-4-yl)-1H-benzimidazole

[0247]

[0248] A mixture of 2-(pyridin-4-yl)-1H-benzimidazole (2.00 g, 10.3 mmol), powdered KOH (0.92 g, 16.4 mmol), and 1-iodohexane (2.39 g, 11.3 mmol) in anhydrous DMSO (30 mL) was stirred at room temperature under N2 for 24 hours, then poured into water (100 mL) and extracted with DCM (3 × 100 mL). The combined extracts were washed with water (100 mL), dried (Na2SO4), and the solvent was removed under reduced pressure. The residue was filtered through silica using EtOAc as the eluent. The solvent was removed under reduced pressure, and the residue was ground with hexane (3 × 50 mL), filtered, washed with hexane, and air-dried to give the title compound (2.53 g, 91%) as a brown powder. H (CDCl3,400MHz)0.77-0.87(3H,m),1.17-1.35(6H,m),1.83-1.96(2H,m),4.450(2H,t,J =7.6), 7.47-7.66(3H,m), 7.90(2H,d,J=6Hz), 7.94(1H,d,J=8Hz) and 8.93(2H,d,J=6Hz); δ C(CDCl3, 100MHz) 13.85, 22.36, 26.26, 29.70, 30.99, 46.00, 111.72, 118.10, 124.02, 126.43, 126.58, 133.56, 134.98, 135.17, 147.07 and 149.00.

[0249] Compound 9: 3-Hexyl-1-methyl-2-(1-methylpyridin-1-onthien-4-yl)-1H-benzimidazole-3-onthienium bis(hexafluorophosphate)

[0250]

[0251] A mixture of 1-hexyl-2-(pyridin-4-yl)-1H-benzimidazole (0.51 g, 1.84 mmol) in MeOTs (1.71 g, 9.2 mmol) was heated at 180 °C for 3 h, cooled, ground with Et₂O (3 × 40 mL), and the residue was air-dried. The residue was dissolved in MeOH (8 mL) and added dropwise with stirring to a solution of NaBF₄ (8.10 g, 73.6 mmol) in water (100 mL). Stirring was continued for 0.5 h. Ammonium hexafluorophosphate (10 g, 61 mmol) was added and stirring was continued for 0.5 h. The resulting precipitate was filtered, washed with water (2 × 10 mL), ground with hot MeOH (40 mL), cooled, filtered, washed with MeOH (5 mL), and air-dried to give the title compound (0.96 g, 87%) as a colorless powder. H [(CD3)2CO,400MHz]0.83(3H,t,J=6.7),1.17-1.45(6H,m),1.93-2.02(2H,m),4.17(3H,s),4.63(2H,t, J=7.7Hz), 4.84(3H,s), 7.87-7.95(2H,m), 8.17-8.33(2H,m), 8.98(2H,d,J=6Hz) and 9.61(2H,d,J=6Hz); δ F [(CD3)2CO,376MHz]-72.687(d,J=710Hz); δ C [(CD3)2CO,100MHz]13.20,22.19,25.80,29.44,31.07,32.82,47.06,49.33,99.81,113.72,113.86,128.01,130.43,131.81,132.86,137.48,145.90 and 147.99.

[0252] Example 10

[0253] 4-(1-Methyl-1H-benzimidazol-2-yl)-1-phenylpyridine-1-onium trifluoromethanesulfonate

[0254]

[0255] A mixture of 1-methyl-2-(pyridin-4-yl)-1H-benzimidazole (1.00 g, 4.8 mmol), diphenyliodonium trifluoromethanesulfonate (3.08 g, 7.2 mmol), and Cu(OAc)₂·H₂O (9.6 mg, 0.48 mmol, 10 mol%) in anhydrous DMF (50 mL) was heated at 100 °C for 16 hours, cooled, and the solvent was removed under reduced pressure. The residue was ground with Et₂O (100 mL), air-dried, and then crystallized from hot MeOH (10 mL). The product was separated by filtration, washed with MeOH, and air-dried to give the title compound (1.33 g, 64%) as a yellow powder. H [(CD3)2CO, 400MHz] 4.294 (3H, s), 7.38–7.45 (1H, m), 7.47–7.53 (1H, m), 7.71–7.90 (5H, m), 8.01–8.11 (2H, m), 8.95 (2H, d, 7Hz) and 9.51 (2H, d, J = 7Hz); δ F [(CD3)2CO, 376MHz] -78.86; δ C [(CD3)2CO,100MHz]32.21,111.26,120.77,123.65,124.62,125.32,127.03,130.60,131.68,138.12,142.98,143.39,144.99,146.72 and 146.88.

[0256] Compound 10: 1,3-Dimethyl-2-(1-phenylpyridin-1-onthien-4-yl)-1H-benzimidazole-3-onthienium bis(tetrafluoroborate)

[0257]

[0258] A mixture of 4-(1-methyl-1H-benzimidazol-2-yl)-1-phenylpyridin-1-onium trifluoromethanesulfonate (0.54 g, 1.2 mmol) in MeOTs (4.62 g, 24.8 mmol) was heated at 180 °C for 3 hours, cooled, and ground with Et2O (50 mL). The residue was filtered off, washed with Et2O (2 × 10 mL), and air-dried. The residue was dissolved in MeOH (10 mL) and added dropwise with stirring to a solution of NaBF4 (2.73 g, 24.8 mmol) in water (50 mL). Stirring was continued for 0.5 hours, and the resulting precipitate was filtered off, washed with water (2 × 5 mL), and air-dried. The residue was ground with hot MeOH (5 mL), filtered, and air-dried to give the title compound (0.49 g, 83%) as a light brown powder. H (DMSO-d6,400MHz)4.04(6H,s),7.80-8.01(7H,m),8.19-8.29(2H,m),8.81(2H,d,J=6.5Hz) and 9.82(2H,d,J=6.5Hz); δ F (DMSO-d6,376MHz)-148.26,-148.20; δ C (DMSO-d6, 100MHz) 33.49, 114.25, 125.24, 128.15, 130.84, 130.99, 132.41, 132.53, 137.83, 142.96, 145.50 and 146.81.

[0259] Example 11

[0260] Compound 11: 1-Hexyl-3-methyl-2-(1-phenylpyridin-1-onthien-4-yl)-1H-benzimidazole-3-onthienium bis(hexafluorophosphate)

[0261]

[0262] A mixture of 1-hexyl-2-(pyridin-4-yl)-1H-benzimidazole (0.8.0 g, 2.9 mmol), diphenyliodonium trifluoromethanesulfonate (1.85 g, 4.3 mmol), and Cu(OAc)₂·H₂O (58 mg, 0.29 mmol, 10 mol%) in anhydrous DMF (30 mL) was heated at 100 °C for 16 hours, cooled, and the solvent was removed under reduced pressure. The residue was ground with Et₂O (3 × 30 mL) and dried under vacuum. The residue was heated in MeOTs (4.26 g, 22.4 mmol) at 180 °C for 2 hours, cooled, and then diluted with Et₂O (80 mL). The solvent was decanted, and the residue was ground with Et₂O (3 × 30 mL) and dried under vacuum. The residue was dissolved in MeOH (20 mL) and added dropwise to a solution of ammonium hexafluorophosphate (4.16 g, 28.7 mmol) in water (100 mL). The precipitate was filtered, washed with water (2 × 10 mL), and air-dried to give the title compound (0.68 g, 38%) as a creamy powder. H [(CD3)2CO,400MHz]0.82(3H,t,J=6.9Hz),1.17-1.45(6H,m),1.96-2.04(2H,m),4.19(3H,s),4.66(2H,t,J=7. 7Hz), 7.81-7.95(5H,m), 7.99-8.10(2H,m), 8.17-8.32(2H,m), 9.13(2H,bd,J=5.2Hz) and 9.89(2H,bd,J=5.2Hz); δ F [(CD3)2CO,376MHz]-72.47(d,J=710Hz); δ C [(CD3)2CO,100MHz]13.31,22.18,25.82,29.49,31.06,32.92,47.14,113.76,113.94,124.76,128.08,130.75,130.95,131.89,132.35,132.96,138.59,143.02,144.71 and 147.04.

[0263] 3. Imidazolo[1,2-a]pyridine

[0264] Example 12

[0265] 7-Bromo-2-phenylimidazo[1,2-a]pyridine A

[0266]

[0267] A mixture of benzoylmethyl bromide (4.00 g, 20.1 mmol), 4-bromopyridin-2-amine (2.90 g, 16.8 mmol), and NaHCO3 (1.69 g, 20.1 mmol) in MeOH (80 mL) was heated under reflux for 5 hours, cooled, and the solvent was reduced. Water (200 mL) was added, and the resulting mixture was extracted with DCM (3 × 100 mL), dried (Na2SO4), and the solvent was removed under reduced pressure. The residue was chromatographically separated on silica using MeOH (5%, in DCM) as the eluent. The solvent was removed under reduced pressure, and the residue was crystallized from DCM / hexane to give the title compound (2.07 g, 39%) as a creamy powder, δ H (CDCl3, 400MHz) 6.91 (1H, dd, J = 1.9 and 7.1Hz), 7.34–7.40 (1H, m), 7.43–7.49 (2H, m), 7.83–7.87 (2H, m), 7.92–7.98 (2H, m) and 8.00 (2H, dd, J = 0.5 and 7.1Hz); δ C (CDCl3, 100MHz) 108.27, 116.34, 118.21, 119.80, 125.72, 126.12, 128.30, 128.80, 133.27, 145.83 and 146.71.

[0268] 2-Phenylacetyl-7-(pyridin-4-yl)imidazo[1,2-a]pyridine C

[0269]

[0270] A mixture of 7-bromo-2-phenylimidazo[1,2-a]pyridine A (1.18 g, 4.3 mmol) and 4-(4,4,5,5-tetramethyl-1,3,2-dioxaborhecyclopentan-2-yl)pyridine (1.32 g, 6.4 mmol), K₂CO₃ (0.90 g, 6.5 mmol), and Pd(PPh₃)₄ (0.20 g, 4 mol%) in degassed PhMe (40 mL) and EtOH (40 mL) was heated under N₂ for 16 hours, cooled, poured into water (50 mL), and extracted with DCM (3 × 40 mL). The combined extracts were dried (Na₂SO₄) and the solvent was removed under reduced pressure. The residues were chromatographically separated on silica using MeOH (5%, in DCM) as the eluent. The band with Rf = 0.5 was collected, the solvent was removed, and the residue was ground with hot PhMe (15 mL). After cooling, the product was collected and air-dried to give the title compound (1.02 g, 87%) as a creamy powder, δ H(CDCl3, 400MHz) 7.12 (1H, dd, J = 1.6 and 7Hz), 7.35-7.42 (1H, m), 7.45-7.52 (2H, m), 7.59 (2H, dd, J = 1.5 and 4.6Hz), 7.94-8.03 (4H, m), 8.25 (1H, dd, J = 0.9 and 7Hz) and 8.74 (2H, dd, J = 1.4 and 4.7Hz); δ C (CDCl3, 100MHz) 108.43, 111.29, 115.22, 120.96, 125.90, 126.12, 128.34, 128.83, 133.42, 134.26, 145.67, 145.87, 147.38 and 150.66.

[0271] 1-Hexyl-4-(2-phenylimidazo[1,2-a]pyridin-7-yl)pyridin-1-onium iodide F

[0272]

[0273] A mixture of 2-phenyl-7-(pyridin-4-yl)imidazo[1,2-a]pyridine C (1.02 g, 3.8 mmol) and 1-iodohexane (2.39 g, 11.3 mmol) in MeCN (40 mL) was heated under reflux for 16 hours, cooled, the solvent was reduced, and the mixture was diluted with Et2O (50 mL). The precipitate was filtered, washed with Et2O (2 × 30 mL), and air-dried to give the title compound (1.81 g, 99%) as an orange powder. H (CD3OD,400MHz)0.94(3H,t,J=6.9Hz),1.32-1.51(6H,m),2.00-2.14(2H,m),4.63(2H,t,J=7.4Hz),7.37-7.57(4H,m) ,7.99(2H,d,J=7.9Hz), 8.29(1H,s), 8.43(1H,s), 8.53(2H,d,J=6.3Hz), 8.68(1H,d,J=7.1Hz) and 9.01(2H,d,J=6.3Hz); δ C (CD3OD, 100MHz) 12.85, 22.08, 25.50, 30.91, 30.98, 60.92, 110.62, 110.81, 116.23, 124.51, 125.89, 127.48, 128.49, 128.61, 130.34, 132.67, 144.53 and 153.97

[0274] 1-Hexyl-4-(2-phenylimidazo[1,2-a]pyridin-7-yl)pyridin-1-onium tetrafluoroborate

[0275]

[0276] With stirring, a solution of 1-hexyl-4-(2-phenylimidazo[1,2-a]pyridin-7-yl)pyridin-1-onium iodide F (1.81 g, 3.7 mmol) in MeOH (20 mL) was added dropwise to a solution of NaBF4 (2.47 g, 22.4 mmol) in water (100 mL). Stirring was continued for 0.5 hours, and the resulting precipitate was filtered, washed with water (5 mL), and air-dried to give the title compound (1.66 g, 100%) as a golden powder, which was used in the next step without further purification.

[0277] Compound 12 7-(1-Hexylpyridin-1-onthien-4-yl)-1-methyl-2-phenylimidazo[1,2-a]pyridin-1-onthienium bis(tetrafluoroborate)

[0278]

[0279] A mixture of 1-hexyl-4-(2-phenylimidazo[1,2-a]pyridin-7-yl)pyridin-1-onium tetrafluoroborate (1.66 g, 3.7 mmol) and MeOTs (2.79 g, 15 mmol) was heated at 180 °C for 2 hours, cooled, ground with Et₂O (3 × 50 mL), and air-dried. The residue was dissolved in MeOH (25 mL) and added dropwise to a solution of NaBF₄ (16.48 g, 150 mmol) with stirring. The resulting precipitate was filtered, washed with water (5 mL), and then dissolved in warm MeOH (50 mL) and added dropwise to a solution of NaBF₄ (16.48 g, 150 mmol) in water (250 mL) with stirring. Stirring was continued for 0.5 hours, and the resulting precipitate was filtered. The residue was ground with EtOH (3 ml), filtered, and air-dried to give the title compound (0.38 g, 19%) as a pale green powder. An ethanol solution was added dropwise to a solution of NaBF4 (16.48 g, 150 mmol) in water (50 mL) with stirring. The resulting precipitate was filtered, washed with water (10 mL), and air-dried to give a second batch of product (0.45 g, 22%) as a khaki powder; δ H[(CD3)2CO,400MHz]0.88(3H,t,J=6.8Hz),1.26-1.55(6H,m),2.12-2.27(2H,m),4.26(3H,s),4.91(2H,t,J=7.2Hz),7.70(3H,bs),7.8 2(2H,bs), 8.26(1H,bs,J=6.6Hz), 8.69(1H,bs), 8.86(2H,bd,J=5.8Hz), 9.05(1H,bs), 9.21(1H,bd,J=6.6Hz) and 9.34(2H,bd,J=5.8Hz); δ F (CDCl3,376MHz)-151.02,-150.97; δ C (CDCl3, 100MHz) 13.31, 22.16, 25.54, 30.98, 31.26, 32.42, 61.73, 111.65, 113.97, 116.12, 125.24, 126.39, 129.44, 130.01, 130.29, 131.13, 138.32, 140.23, 140.38, 145.62 and 151.68.

[0280] Example 13

[0281] 7-Bromo-2-(pyridin-4-yl)imidazo[1,2-a]pyridine B

[0282]

[0283] A mixture of 4-(bromoacetyl)pyridine hydrobromide (8.00 g, 28.5 mmol), 4-bromopyridine-2-amine (4.1 g, 23.7 mmol), and NaHCO3 (4.78 g, 56.9 mmol) in MeOH (80 mL) was heated under reflux for 5 hours, cooled, and the solvent volume was reduced. Water (200 mL) was added, and the resulting mixture was extracted with DCM (3 × 150 mL), dried (Na2SO4), and the solvent was removed under reduced pressure. The residue was chromatographically separated on silica using MeOH (5%, in DCM) as the eluent. A fluorescent band with Rf = 0.6 (5% MeOH, in DCM) was collected. The solvent was removed under reduced pressure, and the residue was crystallized from MeOH (5 mL) at 3 °C, filtered, and air-dried to give the title compound (0.68 g, 10%) as a light brown powder. H(CDCl3, 400MHz) 6.96 (1H, dd, J = 1.7 and 7.2Hz), 7.82 (2H, d, J = 6Hz), 7.86 (1H, bs), 8.00 (1H, bs), 8.04 (1H, d, J = 7.2Hz) and 8.69 (2H, d, J = 6Hz); δ C (CDCl3, 100MHz) 110.02, 117.09, 119.21, 120.19, 120.33, 125.95, 140.69, 143.88, 146.07 and 150.40.

[0284] 7-Phenylacetyl-2-(pyridin-4-yl)imidazo[1,2-a]pyridine D

[0285]

[0286] A mixture of 7-bromo-2-(pyridin-4-yl)imidazo[1,2-a]pyridine B (1.17 g, 4.3 mmol) and phenylboronic acid (0.78 g, 6.4 mmol), K₂CO₃ (0.88 g, 6.4 mmol), and Pd(PPh₃)₄ (0.25 g, 5 mol%) in degassed PhMe (30 mL) and EtOH (30 mL) was heated under reflux at N₂ for 24 h, cooled, poured into water (100 mL), and extracted with DCM (3 × 80 mL). The extract was dried (Na₂SO₄) and the solvent was removed under reduced pressure. The residue was chromatographically separated on silica using MeOH (5%, in DCM) as the eluent. The solvent was removed under reduced pressure, and the residue was ground with hexane containing a few drops of DCM. The residue was filtered off, washed with hexane, and air-dried to give the title compound (1.02 g, 88%) as a light brown powder. H (CDCl3, 400MHz) 7.16 (1H, dd, J = 1.6 and 7Hz), 7.41–7.57 (2H, m), 7.66–7.72 (2H, m), 7.83–7.92 (3H, m), 8.03 (1H, s), 8.21 (1H, d, J = 7Hz) and 8.70 (2H, d, J = 6Hz); δ C (CDCl3, 100MHz) 109.55, 113.14, 114.54, 120.29, 125.66, 126.74, 128.53, 129.19, 138.40, 138.57, 141.16, 143.81, 146.49 and 150.37.

[0287] 1-Hexyl-4-(7-phenylimidazo[1,2-a]pyridin-2-yl)pyridin-1-onium iodide G

[0288]

[0289] A mixture of 7-phenyl-2-(pyridin-4-yl)imidazo[1,2-a]pyridine D (1.00 g, 3.7 mmol) and 1-iodohexane (2.62 g, 12.4 mmol) in MeCN (40 mL) was heated under reflux for 16 hours, cooled, diluted with Et2O (100 mL), and stirred for 0.5 hours. The resulting precipitate was filtered, washed with Et2O (3 × 40 mL), and air-dried to give the title compound (1.73 g, 97%) as a dark yellow powder. H (CD3OD,400MHz)0.95(3H,t,J=6.8Hz),1.32-1.54(6H,m),2.00-2.13(2H,m),4.61(2H,t,J=7.3Hz),7.40-7.59(4H, δ C (CD3OD, 100MHz) 12.85, 22.07, 25.49, 30.90, 60.82, 112.96, 114.05, 115.63, 123.02, 126.49, 127.25, 128.74, 128.94, 137.62, 138.98, 140.88, 144.41, 147.30 and 149.56.

[0290] Compound 13: 2-(1-Hexylpyridin-1-onthien-4-yl)-1-methyl-7-phenylimidazo[1,2-a]pyridin-1-onthienium bis(tetrafluoroborate)

[0291]

[0292] A solution of 1-hexyl-4-(7-phenylimidazo[1,2-a]pyridin-2-yl)pyridin-1-onium iodide G (1.73 g, 3.8 mmol) in MeOH (50 mL) was added dropwise to NaBF4 (10.00 g, 90 mmol) in water (100 mL) with stirring and filtered through a cotton plug. Stirring continued for 0.5 h, and the resulting precipitate was collected by filtration, washed with water (2 × 5 mL), and air-dried. The resulting solid and MeOTs (2.87 g, 15.4 mmol) were heated at 180 °C with stirring for 2 h. The resulting oily substance was cooled, ground with Et2O (5 × 50 mL), and air-dried. The resulting colloidal solid was dissolved in MeOH (30 mL) and added dropwise to a solution of NaBF4 (7.54 g, 68.5 mmol) in water (100 mL) with stirring. Stirring continued for 0.5 hours, and the resulting precipitate was collected, dissolved in hot MeOH (60 mL), and added dropwise to NaBF4 (7.54 g, 68.5 mmol) in water (100 mL) with stirring. Stirring continued for 0.5 hours, and the resulting precipitate was filtered, washed with water (2 × 10 mL), and air-dried. The solid was crystallized from hot MeOH (30 mL), filtered, and air-dried to give the title compound (1.37 g, 74%) as a brownish-red powder. H [(CD3)2CO,400MHz]0.90(3H,t,J=7Hz),1.29-1.59(6H,m),2.16-2.28(2H,m),4.41(3H,s),4.96(2H,t,J=7.5Hz),7.59-7.6 9(3H,m),8.02-8.16(3H,m),8.65(1H,bs),8.70(2H,d,J=6.2Hz), 9.02(1H,bs),9.12(1H,d,J=7Hz) and 9.41(2H,d,J=6.2Hz); δ F [(CD3)2CO,376MHz]-151.24,-151.18; δ C [(CD3)2CO,100MHz]13.29,22.14,25.54,30.98,31.25,32.80,62.15,107.70,116.81,117.43,127.72,128.36,129.55,130.05,130.73,133.24,135.84,142.18,142.50,145.77 and 147.56.

[0293] Example 14

[0294] 2,7-Bis(pyridin-4-yl)imidazo[1,2-a]pyridine E

[0295]

[0296] A mixture of 7-bromo-2-(pyridin-4-yl)imidazo[1,2-a]pyridine B (1.25 g, 4.6 mmol) and 4-(4,4,5,5-tetramethyl-1,3,2-dioxaborhecyclopentan-2-yl)pyridine (1.22 g, 5.9 mmol), K₂CO₃ (0.82 g, 5.9 mmol), and Pd(PPh₃)₄ (0.26 g, 5 mol%) in degassed PhMe (30 mL) and EtOH (30 mL) was heated under reflux at N₂ for 16 hours, cooled, and the solvent was removed under reduced pressure. The residue was washed with water (3 × 50 mL) and air-dried. The residue was chromatographically separated using a gradient of Et3N (10%, in DCM) to Et3N / MeOH / DCM (12 / 3 / 85) as eluents on silica (pretreated with 10% Et3N in DCM). The fractions were evaporated under reduced pressure, and the residue was ground with hexane. The resulting solid was dissolved in MeOH (10 mL), and water (100 mL) was added. The resulting precipitate was filtered, washed with water, and air-dried to give a yellow powder, which was used in the next step without further purification. H (CD3OD, 400MHz) 7.38 (1H, dd, J = 1.7 and 7.2Hz), 7.84 (2H, d, J = 6.3Hz), 7.96 (2H, d, J = 6.2Hz), 7.98 (1H, bs), 8.51 (1H, bs), 8.54–8.62 (2H, m) and 8.65 (2H, d, J = 6.2Hz); δ C (CD3OD, 100MHz) 111.88, 111.99, 114.05, 120.46, 121.38, 127.36, 135.64, 141.74, 142.94, 145.89, 146.28, 149.28 and 149.58.

[0297] 4,4'-(imidazo[1,2-a]pyridine-2,7-diyl)bis(1-hexylpyridine-1-onium)bis(tetrafluoroborate)H

[0298]

[0299] A solution of 2,7-bis(pyridin-4-yl)imidazo[1,2-a]pyridine E (0.80 g, 2.9 mmol) and 1-iodohexane (3.74 g, 17.6 mmol) in MeCN (50 mL) was heated under reflux for 16 hours, cooled, the volume of solvent was reduced (approximately 20 mL), and Et₂O (60 mL) was added. The resulting precipitate was filtered, washed with Et₂O (2 × 30 mL), and air-dried to give 1.69 g. The yellow powder dissolved in MeOH (60 mL) was added dropwise to NaBF₄ (6.47 g, 58.8 mmol) in water (300 mL) with stirring and filtered through a cotton plug. The resulting precipitate was filtered, washed with ice-cold water (2 × 20 mL), and air-dried to give the title compound (1.32 g, 72%) as a green fluorescent powder. H (DMSO-d6, 400MHz) 0.83-0.94 (6H,m), 1.24-1.39 (12H,m), 1.90-2.03 (4H,m), 4.54-4.65 (4H,m), 7.75 (1H,dd,J=1.4 and 7.3Hz), 8.62-8.76 (5H,m), 8.93 (2H,d,J=7.2Hz), 9.10 (2H,d,J=6.7Hz), 9.16 (1H,bs) and 9.20 (2H,d,J=6.7Hz); δ F (DMSO-d6,376MHz)-148.21,-148.16; δ C (DMSO-d6, 100MHz) 14.31, 14.32, 22.34, 22.35, 25.57, 25.59, 31.02, 31.07, 31.10, 60.57, 60.61, 112.43, 117.54, 118.58, 123.59, 125.09, 129.20, 132.08, 141.17, 145.40, 145.51, 145.89, 148.60 and 152.42.

[0300] Compound 14 4,4'-(1-methylimidazo[1,2-a]pyridine-1-onthium-2,7-diyl)bis(1-hexylpyridine-1-onthium)tris(tetrafluoroborate)

[0301]

[0302] A mixture of 4,4'-(imidazo[1,2-a]pyridine-2,7-diyl)bis(1-hexylpyridin-1-onium)bis(tetrafluoroborate) (1.17 g, 1.9 mmol) and MeOTs (2.83 g, 15.2 mmol) was heated at 180 °C for 2 hours, cooled, and ground with Et₂O (50 mL). The residue was filtered and dried under vacuum to give 1.85 g. The solid was dissolved in MeOH (30 mL) and added dropwise with stirring to a solution of NaBF₄ (30 g, 270 mmol) in water (250 mL). Stirring was continued for 0.5 hours, and the resulting precipitate was filtered, washed with water (2 × 5 mL), and air-dried. The residue was dissolved in MeOH / H₂O (30 mL, 1:1) and added dropwise with stirring to a solution of NaBF₄ (20 g, 182 mmol) in water (150 mL). Continue stirring for 0.5 hours, filter the resulting precipitate, wash with water (2 × 5 mL) and air dry to give the title compound (0.99 g, 73%) as a gray powder, δ H [(CD3)2CO,400MHz]0.84-0.96(6H,m),1.27-1.59(12H,m),2.16-2.28(4H,m),4.42(3H,s),4.91-5.04(4H,m),8.33(1H,bd,J=6.7Hz δ F [(CD3)2CO,376MHz]-151.17,-151.12; δ C [(CD3)2CO,100MHz]13.29,22.14,25.54,30.98,31.25,31.28,33.13,61.85,62.27,111.97,116.76,117.63,126.64,128.75,130.89,134.01,140.01,141.69,141.84,145.70,145.85 and 151.48.

[0303] 4. phenimazole

[0304] Example 15

[0305] 6,9-Dibromo-1,2-bis[4-(tert-butyl)phenyl]-1H-phenanthro[9,10-d]imidazole

[0306]

[0307] Acetic acid (100 mL) was added to a stirred mixture of 4-tert-butylaniline (2.20 g, 14.6 mmol, 2.35 mL, 1.5 equivalence) and 4-tert-butylbenzaldehyde (1.58 g, 9.75 mmol, 1.53 mL), followed by the addition of 3,6-dibromophenanthrene-9,10-dione (3.58 g, 9.75 mmol) and ammonium acetate (9.38 g, 122 mmol, 12.5 equivalence), and the mixture was heated under reflux for 2 days at argon atmosphere. Methanol (20 mL) was carefully added, followed by water, until the solution became turbid. After cooling, the precipitate was collected by vacuum filtration and thoroughly washed with a 1:1 water:methanol solution to give the title compound (6.20 g, 99%) as a green powder. H (CDCl3, 400MHz) 1.29 (9H,s), 1.45 (9H,s), 6.96 (1H,d,J=8.9Hz), 7.30 (2H,app d,J=8.5Hz), 7.37 (1H,dd,J=1.9 and 8.9Hz), 7.40 (2H,app.d,J=8.5Hz), 7.51 (2H,app.d,J=8.5Hz), 7.61 (2H,app.d,J=8.5Hz), 7.83 (1H,dd,J=1.7 and 8.5Hz) and 8.69–8.76 (3H,m); δ C (CDCl3, 100MHz) 31.16, 31.41, 34.70, 35.07, 119.07, 119.84, 122.01, 122.35, 124.59, 125.25, 125.95, 126.17, 126.84, 127.18, 127.22, 128.00, 128.41, 128.63, 128.88, 129.53, 129.89, 130.87, 135.61, 137.06, 151.67, 152.23 and 153.56.

[0308] 1,2-Bis[4-(tert-butyl)phenyl]-6,9-bis(pyridin-4-yl)-1H-phenanthro[9,10-d]imidazole

[0309]

[0310] 6,9-Dibromo-1,2-bis-[4-(tert-butyl)phenyl]-1H-phenanthro[9,10-d]imidazole (5.25 g, 8.20 mmol), 4-(4,4,5,5-tetramethyl-1,3,2-dioxaborhecyclopentan-2-yl)pyridine (3.53 g, 17.22 mmol, 2.1 equivalents), Pd(PPh3)4 (0.34 g, 0.287 mmol, 3.5 mol%) and K2CO3 (3.74 g, 17.22 mmol, 2.1 equivalents) were extracted in degassed PhMe / EtOH (1:1, 120 mL) for 5 days. After extraction and subsequent solvent removal, the residue was slurried with DCM and passed through silica, followed by MeOH. The solvent was removed under vacuum, the residue was ground with Et₂O, and the resulting solid was collected by vacuum filtration and air-dried to give the title compound (4.28 g, 82%) as a dark powder. δ H (CDCl3,400MHz)1.31(9H,s),1.48(9H,s),7.27(1H,d,J=8.5Hz),7.32(2H,d,J=8.5Hz),7.47(2H,d,J=8.4Hz),7.55-7.58(3H,m) ,7.64-7.67(4H,m),7.75(2H,d,J=6Hz),8.01(1H,dd,J=1.2 and 8.3Hz),8.72(2H,d,J=6Hz),7.76(2H,d,J=6Hz),8.95-9.03(3H,m); δ C (CDCl3, 100MHz) 31.18, 31.45, 34.73, 35.11, 121.74, 121.78, 121.81, 122.02, 122.48, 123.70, 123.95, 125.29, 125.33, 126.32, 127.20, 127.36, 127.92, 128.39, 128.50, 128.57, 128.92, 129.28, 134.30, 135.29, 135.80, 137.70, 148.25, 148.84, 150.41, 150.42, 151.97, 152.27 and 153.55

[0311] Compound 15 : 4,4'-([1,2-bis(4-(tert-butyl)phenyl]-3-methyl-1H-phenanthro[9,10-d]imidazol-3-onthium-6,9-diyl)bis(1-methylpyridin-1-onthium)tris(tetrafluoroborate)

[0312]

[0313] While stirring under argon, a mixture of 1,2-bis[4-(tert-butyl)phenyl]-6,9-bis(pyridin-4-yl)-1H-phenanthro[9,10-d]imidazole (1.27 g, 2.0 mmol) and MeOTs (3.36 g, 18 mmol, 9.0 equivalents) was heated to 180 °C for 8 hours. After cooling, the mixture was ground with Et2O, and the solid was collected by vacuum filtration to obtain a gray powder (2.75 g). While stirring under argon, a mixture of the crude product (1.17 g) and MeOTs (3.6 g) was heated to 180 °C for 32 hours. After cooling, the mixture was ground with Et2O, and the solid was collected by vacuum filtration. A filtered solution of the solid in hot 1:1 MeOH:water was added dropwise to a solution of NaBF4 (2.64 g, 24 mmol, 12.0 equivalent) in water (25 mL) with stirring to give the title compound (0.71 g, 36%) as a green powder. H (DMSO-d6, 400MHz) 1.28 (9H,s), 1.35 (9H,s), 4.39 (3H,s), 4.45 (6H,bs), 7.19 (1H,d,J=8.8Hz), 7.59-7.77 (9H,m), 8.26 (1H,dd,J=1.5 and 8.9Hz), 8.65 (1H,dd,J=1.5 and 8.9Hz), 8.85 (2H,app.d,J=7Hz), 8.95 (2H,app.d,J=6.7Hz), 9.10-9.22 (5H,m), 9.88 (1H,d,J=1.5Hz) and 9.93 (1H,d,J=1.6Hz). δ F (DMSO-d6, 376MHz) -148.26 and -148.21; δ C (DMSO-d6,100MHz)31.17,31.39,35.40,38.42,47.76,47.83,118.83,122.65 ,122.76,123.48,124.70,125.48,125.64,125.78,126.23,126.36,127.19,12 7.65, 127.90, 128.27, 128.42, 128.53, 130.25, 130.36, 131.57, 132.61, 133.41, 133.51, 138.02, 146.12, 146.25, 151.71, 153.58, 153.72, 155.16 and 155.90.

[0314] Example 16

[0315] 5,10-Dibromo-1,2-bis[4-(tert-butyl)phenyl]-1H-phenanthro[9,10-d]imidazole

[0316]

[0317] Acetic acid (100 mL) was added to a stirred mixture of 4-tert-butylaniline (2.20 g, 14.6 mmol, 2.35 mL, 1.5 equivalence) and 4-tert-butylbenzaldehyde (1.58 g, 9.75 mmol, 1.53 mL), followed by the addition of 2,7-dibromophenanthrene-9,10-dione (3.58 g, 9.75 mmol) and ammonium acetate (9.38 g, 122 mmol, 12.5 equivalence), and the mixture was heated under reflux in argon for 2 days. Methanol (20 mL) was carefully added, followed by water, until the solution became turbid. After cooling, the precipitate was collected by vacuum filtration and washed with a 1:1 water:methanol mixture to give a brownish-red powder. The crude material was purified by column chromatography (pure DCM) to give the title compound (2.74 g, 44%) as a grayish-white powder, δ H (CDCl3,400MHz)1.30(9H,s),1.47(9H,s),6.91(1H,d,J=1.9Hz),7.33(2H,d,J=8.5Hz),7.41(2H,d,J=8.3Hz),7.52(1H,dd,J=1.9 and 8.7H z), 7.62 (2H, d, J = 8.5Hz), 7.66 (2H, d, J = 8.3Hz), 7.69 (1H, dd, J = 2 and 9Hz), 8.42 (1H, d, J = 8.7Hz), 8.47 (1H, d, J = 9Hz) and 9.00 (1H, d, J = 2Hz); δ C (CDCl3, 100MHz) 31.17, 31.43, 34.73, 35.12, 120.83, 122.00, 123.76, 124.26, 124.76, 125.36, 125.41, 125.35, 127.05, 127.16, 127.22, 127.34, 127.76, 127.92, 128.38, 128.58, 128.79, 128.84, 135.41, 137.02, 151.40, 152.31 and 153.90.

[0318] 1,2-Bis[4-(tert-butyl)phenyl]-5,10-bis(pyridin-4-yl)-1H-phenanthro[9,10-d]imidazole

[0319]

[0320] 5,10-Dibromo-1,2-bis[4-(tert-butyl)phenyl]-1H-phenanthro[9,10-d]imidazole (2.63 g, 4.10 mmol), 4-(4,4,5,5-tetramethyl-1,3,2-dioxaborhexacyclopentan-2-yl)pyridine (1.77 g, 8.61 mmol, 2.1 equivalents), Pd(PPh3)4 (0.17 g, 0.14 mmol, 3.5 mol%) and K2CO3 (1.87 g, 8.61 mmol, 2.1 equivalents) were extracted and subsequently solvent-removed, and the solid was crystallized from hot PhMe to give the title compound (1.33 g, 51%) as a green powder, δ H (CDCl3,400MHz)1.31(9H,s),1.49(9H,s),7.22(2H,dd,J=1.5,4.6Hz),7.35(2H,app. d,J=8.5Hz),7.50-7.56(3H,m),7.60(2H,app.d,J=8.5Hz),7.69(2H,app.d,J=8.8.5Hz ),7.80-7.86(3H,m),7.95(1H,dd,J=2,8.6Hz),8.57(2H,dd,J=1.4,4.6Hz),8.76(2H,d d,J=1.4,4.6Hz),8.81(1H,d,J=8.8Hz),8.86(1H,d,J=8.8Hz),9.21(1H,d,J=1.9Hz); δ C (CDCl3, 100MHz) 31.17, 31.51, 34.74, 35.13, 119.32, 121.08, 121.22, 121.94, 123.00, 123.78, 124.08, 124.33, 125.17, 125.38, 127.27, 127.32, 128.00, 128.10, 128.24, 128.60, 128.94, 129.05, 135.25, 135.98, 136.95, 137.81, 147.45, 147.93, 150.27, 150.38, 151.60, 152.30 and 153.66.

[0321] Compound 16: 4,4'-([1,2-bis(4-(tert-butyl)phenyl]-3-methyl-1H-phenanthro[9,10-d]imidazol-3-onthium-5,10-diyl)bis(1-methylpyridin-1-onthium)tris(tetrafluoroborate)

[0322]

[0323] While stirring under argon atmosphere, a mixture of 1,2-bis[4-(tert-butyl)phenyl]-5,10-bis(pyridin-4-yl)-1H-phenanthro[9,10-d]imidazole (0.50 g, 0.79 mmol) and MeOTs (2.21 g, 11.9 mmol, 15 equivalences) was heated to 180 °C for 24 hours, cooled, ground with Et₂O, and the solid was collected by vacuum filtration. The filtered solution of the solid in hot 4:1 MeOH:H₂O was slowly added to a stirred solution of NaBF₄ (0.78 g, 7.11 mmol, 9.0 equivalences) in water (15 mL) and stirred for 30 minutes. The precipitate was collected by vacuum filtration and washed with water to give the title compound (0.65 g, 86%) as a green powder, δ H (DMSO-d6,400MHz)1.27(9H,s),1.32(9H,s),4.35(3H,s),4.43(3H,s),4.57(3H,s), 7.56(1H,d,J=1.7Hz),7.63(2H,d,J=8.5Hz),8.69-7.82(6H,m),7.98(2H,d,J=6.8Hz ), 8.44 (1H, dd, J = 1.7 and 8.8 Hz), 8.60 (1H, dd, J = 1.3 and 8.8 Hz), 8.88 (2H, d, J = 6.8 Hz), 8. 96(2H,d,J=6.8Hz),9.17(2H,d,J=6.8Hz),9.28(1H,d,J=1.2Hz),9.47-9.57(2H,m); δ F (DMSO-d6, 376MHz) -148.25 and -148.2; δ C (DMSO-d6,100MHz)31.16,31.52,35.40,35.41,38.06,47.83,47.89,118.85, 121.13,121.70,122.46,123.15,124.81,125.76,125.90,126.38,126.92,12 7.30, 127.65, 127.80, 127.87, 127.95, 128.38, 128.67, 131.03, 131.32, 131.61, 132.63, 134.18, 134.99, 146.26, 151.19, 153.50, 153.72, 155.16 and 155.89.

[0324] Example 17

[0325] 6,9-Dibromo-1-[4-(tert-butyl)phenyl]-2-(pyridin-4-yl)-1H-phenanthro[9,10-d]imidazole

[0326]

[0327] Acetic acid (100 mL) was added to a stirred mixture of 4-pyridinecarboxaldehyde (1.04 g, 9.75 mmol, 0.91 mL) and 4-tert-butylaniline (2.20 g, 14.6 mmol, 2.35 mL, 1.5 equivalences), followed by the addition of 3,6-dibromophenanthrene-9,10-dione (3.58 g, 9.75 mmol) and ammonium acetate (9.38 g, 122 mmol, 12.5 equivalences), and the mixture was heated under reflux for 3 days at argon atmosphere. Methanol (20 mL) was carefully added, followed by water, until the solution became turbid. After cooling, the precipitate was collected by vacuum filtration, washed with 1 M K₂CO₃ solution, and air-dried to give the title compound (4.76 g, 83%) as a green powder. H (CDCl3, 400MHz) 1.47 (9H, s), 6.99 (1H, d, J = 8.9Hz), 7.37–7.56 (5H, m), 7.66 (2H, d, J = 8.5Hz), 7.84 (1H, dd, J = 1.8 and 8.5Hz), 8.54 (2H, d, J = 6.2Hz) and 8.65–8.75 (3H, m); δ C (CDCl3, 100MHz) 154.42, 149.94, 148.27, 137.89, 137.36, 134.98, 131.13, 130.17, 129.05, 128.82, 128.24, 128.10, 127.59, 126.99, 126.06, 125.31, 124.51, 122.74, 122.47, 121.71, 120.39, 119.91, 35.19 and 31.40.

[0328] 1-[4-(tert-butyl)phenyl]-2,6,9-tris(pyridin-4-yl)-1H-phenanthro[9,10-d]imidazole

[0329]

[0330] 6,9-Dibromo-1-(4-(tert-butyl)phenyl)-2-(pyridin-4-yl)-1H-phenanthro[9,10-d]imidazolium (2.93 g, 5.00 mmol), 4-(4,4,5,5-tetramethyl-1,3,2-dioxaborhecyclopentan-2-yl)pyridine (2.15 g, 10.5 mmol, 2.1 equivalents), Pd(PPh3)4 (0.20 g, 0.18 mmol, 3.5 mol%) and K2CO3 (1.45 g, 10.5 mmol, 2.1 equivalents) were extracted in degassed PhMe / EtOH (1:1, 120 mL) for 6 days. After extraction and subsequent solvent removal, the residue was milled with water (250 mL) and then with Et2O (50 mL). The resulting solid was dissolved in a hot 10:1 PhMe:EtOH solution, cooled to -20°C overnight, and then concentrated under vacuum. The resulting precipitate was collected by vacuum filtration and washed with Et₂O to give the title compound (1.50 g, 52%) as a brownish-red powder. H (CDCl3,400MHz)1.50(9H,s),7.31(1H,d,J=8.7Hz),7.48-7.51(4H,m),7.56-7.77(7H,m),8.04(1H, dd,J=1.2 and 8.4Hz),8.56(2H,d,J=6.1Hz),8.73(2H,d,6Hz),8.76(2H,d,J=6Hz),8.94-9.05(3H,m); δ C (CDCl3, 100MHz) 31.43, 35.22, 121.81, 121.85, 122.01, 122.03, 122.60, 122.82, 123.38, 123.91, 125.62, 126.62, 127.61, 127.67, 128.19, 128.64, 129.29, 129.82, 135.12, 135.90, 137.63, 137.92, 148.05, 148.61, 149.95, 150.44, 150.47 and 154.42.

[0331] Compound 17: 4,4',4”-{[1-(4-(tert-butyl)phenyl]-3-methyl-1H-phenanthro[9,10-d]imidazol-3-onthium-2,6,9-triyl}tri(1-methylpyridin-1-onthium)tetra(tetrafluoroborate)

[0332]

[0333] While stirring under argon, a mixture of 1-[4-(tert-butyl)phenyl]-2,6,9-tris(pyridin-4-yl)-1H-phenanthro[9,10-d]imidazole (1.17 g, 2.0 mmol) and MeOTs (2.60 g, 14 mmol, 7.0 equivalence) was heated to 180 °C for 16 hours. After cooling, the mixture was ground with Et₂O, and the solid was collected by vacuum filtration. The solid was then ground with a small amount of Et₂O using a pestle and mortar, and ground with Et₂O under air drive to obtain a greenish-yellow powder. While stirring under argon, a mixture of the powder (1.55 g) and MeOTs (1.0 g, 5.4 mmol) was heated to 180 °C for 16 hours. After cooling, the mixture was ground with Et₂O, and the solid was collected by vacuum filtration. The filtered solution of the solid in hot MeOH:water (1:1) was added dropwise to a stirred solution of NaBF4 (2.64 g, 24.0 mmol, 12.0 equivalent) in water (25 mL). The mixture was stirred for 30 minutes, and the precipitate was collected by vacuum filtration to give the title compound (0.71 g, 36%) as a green powder. H (DMSO-d6, 400MHz) 1.38 (9H,s), 4.39 (3H,s), 4.43 (3H,s), 4.45 (3H,s), 4.51 (3H,s), 7.02 (1H,d,J = 8.8Hz), 8.26 (1H,dd,J = 1.8 and 8.8Hz), 8.50 (2H,d,J = 6.8Hz), 8.65 (1H,dd,J = 1.8 and 8.8Hz), 8.84 (2H,d,J = 7.1Hz), 8.95 (2H,d,J = 7Hz), 9.12-9.22 (5H,m), 9.27 (2H,d,J = 7Hz), 9.87 (1H,d,J = 1.8Hz) and 9.93 (1H,d,J = 1.8Hz); δ F (DMSO-d6,376MHz)-148.27,-148.22; δ C (DMSO-d6, 400MHz) 31.41, 35.53, 38.62, 47.81, 47.88, 49.35, 122.24, 122.59, 122.95, 124.97, 125.58, 125.77, 126.37, 127.91, 128.22, 128.36, 128.55, 128.75, 130.62, 130.71, 131.28, 134.02, 134.15, 137.00, 145.64, 146.16, 146.28, 147.59, 153.41, 153.58 and 156.09.

[0334] Example 18

[0335] 6,9-Dibromo-1-[4-(tert-butyl)phenyl]-2-(pyridin-4-yl)-1H-phenanthro[9,10-d]imidazole

[0336]

[0337] Acetic acid (100 mL) was added to a stirred mixture of 4-tert-butylaniline (2.20 g, 14.6 mmol, 2.35 mL, 1.5 equivalence) and 4-bromobenzaldehyde (1.80 g, 9.75 mmol), followed by the addition of 3,6-dibromophenanthrene-9,10-dione (3.58 g, 9.75 mmol) and ammonium acetate (9.38 g, 122 mmol, 12.5 equivalence), and the mixture was heated under reflux in argon for 2 days. Methanol (20 mL) was carefully added, followed by water, until the solution became turbid. After cooling, the precipitate was collected by vacuum filtration and washed with a 1:1 water:methanol solution to give the title compound (6.10 g, 94%) as a green powder. H (CDCl3, 400MHz) 1.45 (9H, s), 6.97 (1H, d, J = 8.9Hz), 7.34–7.44 (7H, m), 7.61 (2H, d, J = 8.4Hz), 7.82 (1H, dd, J = 1.5 and 8.5Hz) and 8.64–8.74 (3H, m); δ C (CDCl3, 100MHz) 31.40, 35.12, 119.40, 120.05, 121.83, 122.34, 123.61, 124.48, 126.00, 126.02, 126.90, 127.37, 128.18, 128.25, 128.68, 129.12, 129.66, 130.01, 130.67, 130.96, 131.49, 135.25, 137.11, 150.33 and 153.93.

[0338] 1-[4-(tert-butyl)phenyl]-6,9-bis(pyridin-4-yl)-2-[4-(pyridin-4-yl)phenyl]-1H-phenanthro[9,10-d]imidazole

[0339]

[0340] 6,9-Dibromo-1-[4-(tert-butyl)phenyl]-2-(4-bromophenyl)-1H-phenanthro[9,10-d]imidazole (5.44 g, 8.20 mmol), 4-(4,4,5,5-tetramethyl-1,3,2-dioxaborhecyclopentan-2-yl)pyridine (5.30 g, 25.8 mmol, 3.15 equivalents), Pd(PPh3)4 (0.34 g, 0.38 mmol, 3.5 mol%) and K2CO3 (5.61 g, 25.8 mmol, 3.15 equivalents) were extracted in degassed PhMe / EtOH (1:1, 120 mL) for 7 days. After extraction and subsequent solvent removal, the residue was dissolved in hot 1:1 DCM:isopropanol, cooled to -20 °C overnight, and then concentrated under vacuum. The resulting precipitate was collected by vacuum filtration and washed with Et₂O to give the title compound (3.73 g, 59%) as a green powder, δ H (CDCl3,400MHz)1.49(9H,s),7.32(1H,d,J=8.6Hz),7.48-7.53(4H,m),7.57-7.62(3H,m),7.64-7.71(4H,m),7.73-7.79(4H,m),8. 06(1H,dd,J=1.4,8.3Hz),8.67(2H,dd,J=1.5,4.6Hz),8.73(2H,dd,J=1.5,4.6Hz),8.77(2H,dd,J=1.5,4.6Hz),8.98-9.07(3H,m); δ C (CDCl3, 100MHz) 31.45, 35.17, 121.46, 121.81, 121.91, 122.05, 122.58, 123.57, 123.93, 125.50, 126.50, 126.84, 127.40, 127.81, 128.23, 128.42, 128.53, 128.87, 129.53, 129.90, 130.98, 134.71, 135.58, 135.62, 137.86, 138.44, 147.30, 148.18, 148.77, 150.38, 150.44, 150.92 and 153.92.

[0341] Compound 18 :4,4'-{1-[4-(tert-butyl)phenyl]-3-methyl-2-(4-(1-methylpyridin-1-onthium-4-yl)phenyl)-1H-phenanthro[9,10-d]imidazol-3-onthium-6,9-diyl}bis(1-methylpyridin-1-onthium)tetra(tetrafluoroborate)

[0342]

[0343] While stirring under argon, a mixture of 1-[4-(tert-butyl)phenyl]-6,9-bis(pyridin-4-yl)-2-[4-(pyridin-4-yl)phenyl]-1H-phenanthro[9,10-d]imidazole (3.29 g, 5.0 mmol) and MeOTs (5.59 g, 30 mmol, 6.0 equivalence) was heated to 180 °C for 16 hours. After cooling, the mixture was ground with Et₂O, and the solid was collected by vacuum filtration. The solid was then ground with a small amount of Et₂O using a pestle and mortar, and ground with Et₂O under air drive to obtain a green powder. While stirring under argon, a mixture of the powder (4.91 g) and MeOTs (4.00 g, 21.5 mmol) was heated to 180 °C for 16 hours. After cooling, the mixture was ground with Et₂O, and the solid was collected by vacuum filtration. The filtered solution of the solid in hot 1:1 MeOH:water was added dropwise to a stirred solution of NaBF4 (6.59 g, 50 mmol, 12.0 equivalent) in water (65 mL). The mixture was stirred for 30 minutes, and the precipitate was collected by vacuum filtration to give the title compound (4.17 g, 78%) as a khaki-green powder. H (DMSO-d6,400MHz)1.35(9H,s),4.36(3H,s),4.39(3H,s),4.44(3H,s),4.48(3H,s),7.09(1H,d, J=8.8Hz),7.75(2H,d,8.6Hz),7.80(2H,d,J=8.6Hz),8.08(2H,d,J=8.4Hz),8.25(1H,dd,J=1.7, 8.9Hz),8.32(2H,d,J=8.5Hz),8.56(2H,d,J=6.9Hz),8.65(1H,dd,J=1.7,8.8Hz),8.85(2H,d,J= 7.1Hz), 8.95(2H,d,J=7.1,Ar-H), 9.05-9.27(7H,m), 9.88(1H,d,J=1.7Hz) and 9.95(1H,d,J=1.7); δ F (DMSO-d6, 376MHz) -148.25 and -148.20; δ C(DMSO-d6, 100MHz) 31.41, 35.45, 38.48, 47.78, 47.84, 122.63, 123.35, 124.77, 125.21, 125.51, 125.67, 125.78, 126.30, 127.41, 127.88, 128.17, 128.43, 128.60, 129.09, 130.35, 130.48, 132.33, 133.04, 133.57, 133.69, 137.67, 147.13, 146.27, 146.43, 150.26, 152.92, 153.51, 153.67 and 155.48.

[0344] 5. benzo[selenazole]

[0345] Example 19

[0346] 4-(benzoselenazole-2-yl)-1-hexylpyridine-1-onium iodide

[0347]

[0348] 2-(pyridin-4-yl)benzoselenazole (0.75 g, 2.89 mmol) and 1-iodohexane (1.23 mL, 8.67 mmol) were suspended in MeCN (40 mL) and then stirred at 80 °C for 16 hours. The reaction mixture was cooled to ambient temperature and the solvent was removed under reduced pressure. The resulting solid was ground with acetone (20 mL), filtered, washed with acetone (20 mL), and dried under reduced pressure to give the desired product as an orange powder. Yield: 1.10 g, 81%. δ H (CD3OD,300MHz)9.11(d,J=6.9Hz,2H),8.68(d,J=6.9Hz,2H),8.28(d,J=8.2Hz,1H),8.23(d,J=8.2Hz,1H),7.65(dd,J=7.3,1.2 Hz,1H),7.53(dd,J=7.3,1.2Hz,1H),4.67(t,J=7.6,2H),1.95(quint.,J=7.4Hz,2H),1.55-1.23(m,6H),0.94(t,J=6.8Hz,3H); δ C (DMSO-d6,100MHz)166.72,156.98,151.53,146.78,142.04,128.82,128.80,127.52,126.90,126.53,62.87,32.41,32.32,26.91,23.48,14.28.

[0349] Compound 19 4-(benzoselenazole-2-yl)-1-hexylpyridine-1-onium tetrafluoroborate

[0350]

[0351] 4-(benzoselenazole-2-yl)-1-hexylpyridin-1-onium iodide (0.65 g, 1.38 mmol) was dissolved in hot MeOH (50 mL) and added dropwise through a cotton plug to a stirred solution of NaBF4 (5.0 g) in H2O (200 mL), thereby forming a pale yellow precipitate. The solution was stirred for 30 minutes and then filtered under reduced pressure. The resulting solid was washed with water (30 mL) and then dried under reduced pressure to give the desired product as a pale yellow powder. Yield: 0.59 g, 76%. δ H (DMSO-d6,400MHz)9.20(d,J=6.7Hz,2H),8.74(d,J=6.7Hz,2H),8.39(d,J=8.0Hz,1H),8.28(d,J=8.0Hz,1H),7.66(dd,J=7.3,0. 9Hz, 1H), 7.55 (dd, J = 7.3, 0.9Hz, 1H), 4.64 (t, J = 7.4, 2H), 1.95 (quint., J = 6.5Hz, 2H), 1.43-1.20 (m, 6H), 0.87 (t, J = 6.7Hz, 3H); δ C (DMSO-d6,100MHz)166.57,154.99,148.64,145.71,140.40,127.61,127 .34,126.49,125.91,125.21,60.57,30.68,30.56,25.05,21.84,13.81; δ B (DMSO-d6, 128MHz)-1.3; δ F (DMSO-d6,376MHz)-148.27(br.m,4F).

[0352] Example 20

[0353] 4-(benzoselenazole-2-yl)-1-phenylpyridine-1-onium trifluoromethane sulfonate

[0354]

[0355] 2-(pyridin-4-yl)benzoselenazole (1.00 g, 3.86 mmol), diphenyliodonium trifluoromethanesulfonate (2.49 g, 5.79 mmol), and Cu(OAc)₂·H₂O (116 mg, 0.58 mmol) were dissolved in DMF (30 mL) under N₂, and the reaction mixture was stirred at 100 °C for 16 hours. The reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. The resulting yellow solid was ground in hot MeOH, filtered, and dried under reduced pressure to give the desired product as a yellow powder. Yield: 1.70 g, 91%. H (DMSO-d6,400MHz)9.46(d,J=6.9Hz,2H),8.86(d,J=6.9Hz,2H),8.42(d,J=7.8Hz,1H),8.33(d,J=7.8H z,1H),8.00-7.90(m,2H),7.84-7.74(m,3H),7.69(dd,J=7.4,1.1Hz,1H),7.58(dd,J=7.4,1.1Hz,1H); δ C (DMSO-d6,100MHz)166.28,155.14,149.35,145.83,142.39,140.80,131. 40,130.24,127.75,127.55,126.60,126.14,124.97,124.68,120.65(d,J C-F =320.4Hz); δ F (DMSO-d6,376MHz)-77.76(s,3F).

[0356] Compound 20 4-(benzoselenazole-2-yl)-1-phenylpyridine-1-onium tetrafluoroborate

[0357]

[0358] 4-(benzoselenazole-2-yl)-1-phenylpyridin-1-onthium trifluoromethane sulfonate (1.00 g, 2.06 mmol) was dissolved in hot MeOH (50 mL) and added dropwise through a cotton plug to a stirred solution of NaBF4 (5.0 g) in H2O (200 mL), thereby forming a yellow precipitate. The solution was stirred for 30 minutes and then filtered under reduced pressure. The resulting solid was washed with water (30 mL) and then dried under reduced pressure to give the desired product as a yellow powder. Yield: 0.61 g, 70%. δ H(DMSO-d6,400MHz)9.45(d,J=6.9Hz,2H),8.55(d,J=6.9Hz,2H),8.41(d,J=7.8Hz,1H),7.32(d,J=7.8H z,1H),8.00-7.87(m,2H),7.83-7.72(m,3H),7.67(dd,J=7.4,1.1Hz,1H),7.57(dd,J=7.4,1.1Hz,1H); δ C (DMSO-d6,100MHz)166.30,155.16,149.36,145.84,142.40,140.82,131.43,130.27,127.77,127.57,126.61,126.16,124.99,124.69; δ B (DMSO-d6, 128MHz)-1.3; δ F (DMSO-d6,376MHz)-148.21(br.m,4F).

[0359] Example 21

[0360] Compound 21 4-(benzoseleno-2-yl)-1-phenylpyridine-1-onium hexafluorophosphate

[0361]

[0362] 4-(benzoselenazole-2-yl)-1-phenylpyridin-1-onthium trifluoromethane sulfonate (0.20 g, 0.47 mmol) was dissolved in hot MeOH (20 mL) and added dropwise through a cotton plug to a stirred solution of NH4PF6 (0.50 g) in H2O (100 mL), thereby forming a yellow precipitate. The solution was stirred for 30 minutes and then filtered under reduced pressure. The resulting solid was washed with water (30 mL) and then dried under reduced pressure to give the desired product as a yellow powder. Yield: 0.13 g, 71%. δ H [(CD3)2CO,400MHz]9.52(d,J=6.3Hz,2H),8.98(d,J=6.3Hz,2H),8.38(d,J=8.5Hz,1H),8.36(d,J =8.5Hz,1H),8.13-7.95(m,2H),7.92-7.78(m,3H),7.73(t,J=7.6Hz,1H),7.61(t,J=7.6Hz,1H); δ C[(CD3)2CO,100MHz]166.22,156.65,151.54,146.67,143.78,141.91,132.64,131.45,128.74,128.71,127.39,126.99,126.34,125.43; δ P [(CD3)2CO,162MHz]-144.27(sept.,J=707.8Hz,1P); δ F [(CD3)2CO,376MHz]-72.51(d,J=707.8Hz,6F).

[0363] 6. Benzoxazole and Benzisoxazole

[0364] Example 22

[0365] 2-(pyridin-4-yl)-2,3-dihydrobenzoxazole

[0366]

[0367] A solution of 2-aminophenol (8.00 g, 73.4 mmol) and pyridine-4-carboxaldehyde (7.85 g, 73.4 mmol) in EtOH (350 mL) was stirred under air for 5 days. The volume of solvent was reduced, and the resulting solid was filtered off, washed with EtOH (20 mL), and air-dried to give the title compound (13.36 g, 92%) as an orange powder. H (CDCl3,400MHz)6.93(1H,app.t,J=7.7Hz),7.04(1H,app.d,J=8.1Hz),7.22-7.31(2 H,m), 7.35(1H,app.d,J=8.0Hz), 7.76(2H,bd,J=4.5Hz), 8.69(1H,s) and 8.78(2H,bs).

[0368] 2-(pyridin-4-yl)benzoxazole

[0369]

[0370] Under stirring, 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (1.15 g, 5 mmol) was added in one step to a solution of 2-(pyridin-4-yl)-2,3-dihydrobenzoxazole (1.00 g, 5 mmol) in DCM (50 mL). Stirring continued for 1 hour, and Et3N (5 mL) was added. The resulting solution was filtered through silica using DCM (100%–0%, in EtOAc) as the eluent. The first band was collected to give the title compound (0.43 g, 43%) as a pale yellow powder. The second band was collected to give unreacted starting material (0.28 g, 28%), δ H (CDCl3, 400MHz) 7.39-7.47 (2H,m), 7.61-7.66 (1H,m), 7.81-7.85 (1H,m), 8.10 (2H,dd,J=1.6 and 4.6Hz) and 8.83 (2H,dd,J=1.6 and 4.6Hz).

[0371] 4-(benzoxazol-2-yl)-1-hexylpyridine-1-onium iodide

[0372]

[0373] A solution of 2-(pyridin-4-yl)benzoxazole (1.00 g, 5.1 mmol) and 1-iodohexane (3.24 g, 15.3 mmol) in MeCN (30 mL) was heated under reflux with stirring in the dark under N2. After 16 hours, the resulting mixture was cooled and diluted with Et2O (50 mL). The precipitate was filtered off, washed with Et2O (3 × 10 mL), and air-dried to give the title compound (2.06 g, 99%) as a yellow powder.

[0374] Compound 22 4-(benzoxazol-2-yl)-1-hexylpyridine-1-onium tetrafluoroborate

[0375]

[0376] A solution of 4-(benzoxazol-2-yl)-1-hexylpyridin-1-onium iodide (2.01 g, 4.9 mmol) in warm MeOH / water (50 mL, 1:1) was added dropwise to a solution of NaBF4 (5.42 g, 40 mmol) in water (100 mL) with stirring. Stirring was continued for 0.5 hours, and the resulting precipitate was filtered off, washed with water (3 × 10 mL), and air-dried to give the title compound (1.77 g, 98%) as a colorless powder. H(CD3OD,400MHz)0.89-0.97(3H,bt,J=5.7Hz),1.30-1.51(6H,m),2.00-2.14(2H,m),4.69(2H,bt,J=7.4Hz),7. 50-7.65(2H,bm), 7.83(1H,bd,J=8.2Hz), 8.93(1H,bd,J=8Hz), 8.78(2H,bd,J=5.5Hz) and 9.16(2H,bd,J=5.5Hz).

[0377] Example 23

[0378] 4-(benzoxazol-2-yl)-1-phenylpyridine-1-onium trifluoromethanesulfonate

[0379]

[0380] A mixture of 2-(pyridin-4-yl)benzoxazole (1 g, 5.1 mmol), diphenyliodonium trifluoromethanesulfonate (3.29 g, 7.6 mmol), and Cu(OAc)₂·H₂O (100 mg, 10 mol%) in anhydrous DMF (50 mL) was heated at 100 °C for 16 hours, cooled, and the solvent was removed under reduced pressure. The residue was ground with Et₂O (50 mL), washed with Et₂O (3 × 10 mL), and air-dried. The resulting solid was ground with hot MeOH (20 mL), cooled, filtered, and air-dried to give the title compound (1.86 g, 86%) as a colorless powder. H (CD3OD, 400MHz) 7.54-7.70 (2H, bm), 7.76-8.00 (7H, bm), 8.93 (2H, bd, J = 5.9Hz) and 9.42 (2H, bd, J = 5.9Hz).

[0381] Compound 23 4-(benzoxazol-2-yl)-1-phenylpyridine-1-onium tetrafluoroborate

[0382]

[0383] A solution of 4-(benzoxazol-2-yl)-1-phenylpyridin-1-onium trifluoromethanesulfonate (0.25 g, 0.59 mmol) in warm MeOH (10 mL) was added dropwise to a solution of NaBF4 (0.65 g, 5.9 mmol) in water (30 mL) under stirring. The resulting precipitate was filtered, washed with water (2 × 3 mL), dissolved in warm MeOH (10 mL), and added dropwise to a solution of NaBF4 (0.65 g, 5.9 mmol) in water (30 mL) while stirring for 0.5 hours. The resulting precipitate was filtered off, washed with water (2 × 3 mL), and air-dried to give the title compound (0.20 g, 95%) as a pale yellow powder. H (DMSO-d6,400MHz)7.56-7.62(1H,m),7.64-7.70(1H,m),7.74-7.82(3H,m),7.91- 8.01(3H,m), 8.05(1H,d,J=7.9Hz), 8.87(2H,bd,J=6.8Hz) and 9.53(2H,bd,J=6.8Hz).

[0384] Example 24:

[0385] 4-(2-Methoxybenzoyl)pyridine

[0386]

[0387] A freshly prepared solution of 2-methoxyphenyl magnesium bromide (40 mL, approximately 1.38 M, 55.4 mmol) was added to a stirred solution of 4-cyanopyridine (2.78 g, 26.7 mmol) in anhydrous THF (20 mL), which had been cooled to 0 °C under N2. After the addition was complete, the reaction mixture was stirred and heated at 50 °C under N2 for 16 hours. The solution was then cooled to 0 °C, and H2O (20 mL) was slowly added. The reaction mixture was then evaporated to dryness under reduced pressure, and 2 M HCl (100 mL) was added, followed by heating at 80 °C for 8 hours. The reaction mixture was then cooled to room temperature, and the solution was washed with EtOAc (2 × 100 mL). The aqueous phase was alkalized with NaOH (5 M) and extracted with DCM (3 × 100 mL). The organic layers were combined, dried (Na2SO4), filtered, and the solvent was removed under reduced pressure. The resulting residue was separated by silica gel chromatography [eluent = 1:9, increasing to 1:1 EtOAc:petroleum ether]. The solvent in the resulting column fraction was removed under reduced pressure to give the title compound as a yellow oil. Yield: 4.60 g, 82%. δ H(CDCl3,400MHz)8.75(2H,dd,J=4.4,1.6Hz),7.57 -7.51(3H,m),7.46(1H,dd,J=7.6,1.8Hz), 7.07(1H,td,J=7.55,0.9Hz), 6.99(1H,d,J=8.3Hz) and 3.68(3H,s); δ C (CDCl3, 100MHz) 195.6, 158.0, 150.5, 144.8, 133.5, 130.5, 127.3, 122.4, 121.0, 111.7 and 55.6.

[0388] 3-(pyridin-4-yl)-1,2-benzoxazole

[0389]

[0390] 4-(2-methoxybenzoyl)pyridine (3.60 g, 16.8 mmol) was dissolved in anhydrous DCM (100 mL) and cooled to 0 °C under N2. BBr3 (8.42 g, 3.24 mL, 33.6 mmol) was added dropwise, and the reaction mixture was stirred for 16 hours. The reaction mixture was added to ice, neutralized with NaHCO3, and stirred for 1 hour. The reaction mixture was then extracted with DCM (2 × 200 mL), and the organic layers were combined, dried (Na2SO4), filtered, and the solvent removed under reduced pressure. The resulting residue was subjected to chromatographic separation on silica gel [eluent = 1:9, increasing to 4:6 EtOAc: petroleum ether]. The solvent in the resulting column fraction was removed under reduced pressure to give an impure 4-(2-hydroxybenzoyl)pyridine (2.60 g) as a yellow solid, which was used in subsequent reactions without further purification. Impure 4-(2-hydroxybenzoyl)pyridine (2.60 g) was dissolved in 7N ammonia in methanol (30 mL) and stirred at room temperature for 48 hours to give an orange solution. The reaction mixture was then evaporated to dryness under reduced pressure and redissolved in anhydrous THF (40 mL) under N2. N-chlorosuccinimide (2.60 g, 19.5 mmol) and K2CO3 (3.60 g, 138 mmol) were then added to the reaction mixture, and the mixture was stirred at room temperature under N2 for 16 hours. The reaction mixture was then diluted with diethyl ether (100 mL) and quenched with water (100 mL). The organic layer was separated, and the aqueous layer was extracted with diethyl ether (2 × 100 mL). The organic layers were combined, dried (Na2SO4), filtered, and the solvent was removed under reduced pressure. The resulting residue was subjected to chromatographic separation on silica gel [eluent = 1:9, increasing to 3:7 EtOAc: petroleum ether]. The solvent in the resulting column fraction was removed under reduced pressure to give a pale yellow solid, which was then ground with pentane and dried under reduced pressure to give the title compound as a grayish-white solid. Yield: 1.2 g, 36%. δ H (CDCl3,400MHz)8.84(2H,dd,J=4.5,1.5Hz),7.95(1H,dt,J=8.0,0.9Hz),7.89(2H,dd,J=4.4,1.6Hz )7.70(1H,dt,J=8.4,0.8Hz), 7.67(1H,ddd,J=8.5,7.0,1.0Hz) and 7.44(1H,ddd,J=8.5,7.0,1.0Hz); δ C (CDCl3,100MHz)164.3,155.4,150.9,136.7,130.4,124.6,122.3,1217,119.9,110.6.

[0391] Compound 24:4-(1,2-Benzisoxazo-3-yl)-1-phenylpyridine-1-onium hexafluorophosphate

[0392]

[0393] 3-(pyridin-4-yl)-1,2-benzoxazole (1.00 g, 5.1 mmol), diphenyliodonium trifluoromethanesulfonate (3.29 g, 7.64 mmol), and Cu(OAc)₂·H₂O (0.1 g, 0.51 mmol) were dissolved in DMF (40 mL) under N₂, and the reaction mixture was stirred at 100 °C for 16 hours. The reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. The resulting pale green solid was ground with diethyl ether (3 × 50 mL), filtered, and dried under reduced pressure. The resulting hygroscopic pale green solid was dissolved in hot MeOH:H₂O (approximately 2:1, 150 mL), and added dropwise through a cotton plug to a stirred solution of NH₄PF₆ (17.5.0 g) in H₂O (350 mL), thereby forming a pale yellow precipitate. The suspension was stirred for 30 minutes and then filtered under reduced pressure. The obtained solid was washed with water (50 mL) and then dried under reduced pressure to give a pale green powder. The solid was then dissolved in hot acetone:H₂O (approximately 2:1, 200 mL) and added dropwise through a cotton plug back to the filtrate (which had been reduced by approximately 20% under vacuum), giving a pale green precipitate. The resulting suspension was then filtered under reduced pressure, and the solid was washed with water (50 mL) and then dried under reduced pressure to give a pale green powder. The green powder was ground with MeOH (50 mL), filtered, and dried under reduced pressure to give the title compound as a colorless powder. Yield: 1.17 g, 55%. δ H (DMSO-d6,400MHz)9.60(2H,d,J=7.0Hz),8.96(2H,d,J=6.9Hz),8.43(1H,d,J=8.1Hz),8.09(1H,d,J=8.6Hz) 8.05-7.98(2H,m),7.93(1H,ddd,J=8.5,7.1,1.0Hz), 7.89-7.79(3H,m) and 7.72(1H,ddd,J=8.5,7.3,0.5Hz); δ C (DMSO-d6, 100MHz) 164.1, 153.3, 146.0, 144.1, 142.5, 131.6, 131.5, 130.3, 126.2, 125.8, 124.8, 122.4, 118.6 and 110.7; δ F (DMSO-d6,376MHz)-170.13(6F,d,J=711.0Hz).

[0394] Evaluation of the redox potential and absorption spectrum of the compounds of this invention

[0395] Methods for measuring redox potential

[0396] The redox potential of the compound was measured using cyclic voltammetry with three electrodes.

[0397] The three electrodes used are:

[0398] -1 platinum working electrode

[0399] -1 platinum auxiliary or counter electrode

[0400] -1 platinum reference electrode, which is immersed in a solution consisting of 0.01M AgNO3 + 0.1MTBAP (tetrabutylammonium perchlorate) in acetonitrile.

[0401] The potential scan rate was fixed at 100 mV / s.

[0402] E1 还原 The first reduction peak corresponds to the compound being analyzed.

[0403] E2 还原 The second reduction peak corresponds to the compound being analyzed.

[0404] E1 1 / 2 The redox potential of the oxidant / reductant system is calculated as follows:

[0405] E1 1 / 2 =(E1) 还原 +E1 氧化 ) / 2

[0406] E1 氧化 The first oxidation peak corresponds to the compound being analyzed.

[0407] ΔE 还原 E1 corresponding to the following calculation 还原 With E2 还原 The difference between them:

[0408] ΔE 还原 =|E2 还原 │-│E1 还原 │.

[0409] The potential values ​​shown are the first reduction potentials of the compound relative to the standard hydrogen reference electrode (SHE).

[0410] The solution analyzed contained 0.005 M of the compound to be analyzed and 0.25 M of TBABF4 salt in propylene carbonate as a solvent.

[0411] Methods for measuring absorption spectra

[0412] This solution is introduced into the quartz cell.

[0413] This solution is introduced into a quartz cell, in which at least one working electrode in the form of a platinum mesh is placed to stain the compound being analyzed. The absorption spectrum of the compound being analyzed is measured in the time domain using ultraviolet-visible spectroscopy.

[0414] The results for each synthesized compound are shown in Table 1 below. E1 还原 This corresponds to the first reduction potential. The colors shown in Table 1 are the visual colors perceived by a normal eye under sunlight conditions. It should be noted that λ... max The value only provides an approximate indication of the color of a particular compound. However, due to the broad nature of absorption bands, the entire absorption spectrum must be considered to understand the final perceived color of any compound.

[0415] In comparison, Table 2 shows the results obtained for the three known compounds.

[0416] By comparing the compounds 2 (orange) and 6-7 (red) of the present invention with the known compound COMP1 (green), it appears that replacing a phenylpyridinium group with a substituted benzimidazolium or substituted benzothiazolium group reduces the maximum absorption wavelength in the visible light range from 645 nm to 550 nm or lower. In their activated state, these molecules are red or orange rather than green.

[0417] By comparing compounds 1, 10, 16 (orange), 3, 4, 5 (purple), 8 (green), 9, 11 (yellow / green), and 13-14 (yellow) with known compounds COMP2 (blue) and COMP3 (blue), it appears that individually containing different groups such as imidazolyl, benzimidazolium, benzothiazolyl, or contained within more complex molecular structures also has this effect of shifting the maximum absorption wavelength to a lower value. These groups can be introduced between two alkyl bispyridinium groups, or the central pyridinium group of a tripyridinium group can be substituted. The resulting molecules are yellow, orange, red, green, or purple instead of blue.

[0418] The results showed that COMP3, a known compound containing a phenyl group between two alkylbispyridinium groups, is also orange, with an activation potential of -1.21 V. Apart from compounds 11 and 14, the compounds of the present invention have similar or lower activation potentials than COMP3.

[0419]

[0420]

[0421]

[0422]

[0423]

Claims

1. An electrochromic device comprising an electrochromic compound represented by formula (I): (I) in: A is + N-R1; B is C-R2; D is S or N-R3; E is C; or A is + N-R1; B is C-R2; D is C-R3; E is N; or A is N; B is C-R2; D is Se or O; E is C; or E is + N; A is O, S, or Se; B is C-R2; D is C-R3; R1 is H, C1-C 18 Alkyl, C6-C 18 Aryl or Z; R2 is H, C1-C 18 Alkyl, C6-C 18 Aryl, Z, or Z-substituted C6-C 18 Aryl; R3 is H or Cl-C 18 Alkyl, C6-C 18 Aryl or Z; R4 is H, C1-C 18 Alkyl, C6-C 18 Aryl or Z; R5 is H, C1-C 18 Alkyl, C6-C 18 Aryl or Z; R6 is H, C1-C 18 Alkyl, C6-C 18 Aryl or Z; R7 is H, C1-C 18 Alkyl, C6-C 18 Aryl or Z; R7 and R6, R6 and R5, or R5 and R4 can together form an aromatic or heteroaromatic ring fused with the ring C6 to which they are attached, which may optionally be substituted with Z. Where Z is ; Y is C1-C 18 Alkyl, C6-C 18 aryl, monocyclic or polycyclic heteroaryl groups comprising 1 to 3 heteroatoms independently selected from oxygen, nitrogen, and sulfur, 5 to 10 members, C1-C 18 C6-C of alkyl groups 18 Aryl derivatives or C1-C 18 Alkyl groups are monocyclic or polycyclic heteroaryl derivatives comprising 1 to 3 heteroatoms independently selected from oxygen, nitrogen, and sulfur, ranging from 5 to 10 members. R8, R9, R 10 and R 11 Independently selected from H and C1-C 18 alkyl; Choose n to counteract the number of positive charges; X is a counter ion; Is it a single bond or a double bond? This requires the following two prerequisites: 1) Rings C5 and C6 form a conjugate system; and 2) At least one of R1, R2, R3, R4, R5, R6 or R7 is Z, or at least R7 and R6 together form an aromatic ring substituted by Z, or at least R5 and R6 together form an aromatic ring substituted by Z, or at least R5 and R4 together form an aromatic ring substituted by Z.

2. The apparatus according to claim 1, wherein, The compounds of formula (I) are represented by formulas (II), (IV), (V), (VI), (VII), (VIII), (IX), or (X): (II) (IV) (V) (VI) (VII) (VIII) (IX) (X) 。 3. The apparatus according to claim 1 or 2, wherein, A is N, or + N-R1.

4. The apparatus according to claim 1 or 2, wherein, E is N or + N and / or D are S.

5. The apparatus according to claim 2, wherein, The compound of formula (I) is of formula (II) and wherein A is N, or + N-R1; D is N-R3, S, Se, or O; and E is C.

6. The apparatus according to claim 5, wherein, D is S.

7. The apparatus according to claim 6, wherein, R7 and R6, R6 and R5, or R5 and R4 together form an aromatic or heteroaromatic ring fused with the ring C6 to which they are connected, which is optionally replaced by Z.

8. The apparatus according to claim 1, wherein, The compounds of formula (I) are selected from: 。 9. The apparatus according to claim 1 or 2, wherein the electrochromic compound is contained in the electrochromic composition.

10. The apparatus according to claim 9, wherein, The composition further comprises a host medium as a fluid, mesocrystalline medium, or gel.

11. The electrochromic device according to claim 1 or 2, wherein, The electrochromic device is an ophthalmic lens.

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