TW201323478A - Fused thiophenes, methods of making fused thiophenes, and uses thereof - Google Patents

Abstract

Described herein are compositions including heterocyclic organic compounds such as fused thiophene compounds, methods for making them, and uses thereof.

Description

And thiophene, method for producing and cyclizing thiophene and use thereof

The present application claims priority to 35 USC § 119 U.S. Provisional Application Serial No. 61/553,326, filed on Jan. 31, 2011, the content of which is hereby incorporated by reference herein in its entirety The way is included in this article.

Described herein are compositions comprising a heterocyclic organic compound. More particularly, what is described herein are a cyclohexaphene compound, a method of making a cyclopentene compound, and the use of a cyclo-thiophene compound.

Highly conjugated organic materials are currently the focus of important research activities, primarily due to the interesting electronic and optoelectronic properties of these highly conjugated organic materials. These highly conjugated organic materials have been investigated for a wide range of applications, including field effect transistors (FETs), thin film transistors (TFTs), organic light emitting diodes (OLEDs), photovoltaic (EO) applications, as conductors. Materials, as two-photon hybrid materials, as organic semiconductors and as nonlinear optical (NLO) materials. Highly conjugated organic materials can find efficacy in, for example, RFID tags, electro-laser devices in flat panel displays, and photovoltaic and sensor devices.

Materials such as pentacycline, poly(thiophene), poly(thiophene-co-extension ethylene), poly(p-phenylene-co-extension ethylene), and oligo(3-hexylthiophene) have been extensively studied for various In electronic and optoelectronic applications. Recently, it has been found that cyclohexaphene compounds have advantageous properties. For example, it has been found that bisdithieno[3,2-b:2 ' , 3'- d]thiophene ( 1 ,j=2) is effectively π-stacked in solid state with high mobility (up to 0.05 cm) ² /V.s) and has a high on/off ratio (up to 10 ⁸ ). Oligomers and polymers of cyclohexaphene, for example, oligo- or poly(thieno[3,2-b]thiophene)( 2 ) and oligo- or poly(dithieno[3,2-b:2 ' -3 ' -d]thiophene)( 1 )

It has also been proposed for use in electronic and optoelectronic devices and has been shown to have acceptable conductivity and nonlinear optical properties. Unsubstituted cyclo-thiophene-based materials have a tendency to suffer from low solubility, critical operability, and oxidative instability. Therefore, there is still a need for a cyclic thiophene-based material having acceptable solubility, operability, and oxidative stability.

Described herein are compositions comprising a heterocyclic organic compound (e.g., a cyclo-thiophene compound), methods of making the foregoing compositions, and compositions of the foregoing use. The compositions and methods described herein have many advantages over prior art compositions and methods. For example, the cyclohexaphene compositions described herein can be made more soluble and more operative than similar unsubstituted thiophene compositions. Polymers or oligomers comprising the cyclophene molecular moieties described herein can be made operable using conventional spin coating operations. In addition, the compositions described herein can also be made substantially free of beta-H content, greatly improving the oxidative stability of the composition.

Other features and advantages will be set forth in the description which follows, and in part in the description which Will be understood.

The above general description and the following detailed description are merely illustrative, and are intended to provide an overview or architecture for understanding the nature and features of the invention.

Before the materials, materials, and/or methods of the present invention are disclosed and illustrated, it is to be understood that the aspects described below are not limited to the particular compounds, methods of construction, or use, as such aspects may of course vary. It is also to be understood that the terminology used herein is for the purpose of description

In the present specification and the scope of the patent application described later, reference may be made to many Nouns, these nouns shall be defined as having the following meanings: In the entire specification, unless the context requires different content, the term "including" or variation (such as "including" or "incorporating") will be understood to imply the inclusion of An integer or a group of steps, integers, or steps, but does not exclude any other integers or steps, or groups of integers or steps.

It must be noted that, as used in the specification and the appended claims, the singular forms "a", "the" Thus, for example, reference to "a pharmaceutical carrier" includes a mixture of two or more such carriers, and the like.

"As needed" or "as needed" means that the subsequently described event or condition may or may not occur, and that the description includes examples of events or conditions and examples of non-occurrence.

Ranges may be expressed herein as "about" a particular value and/or to "about" another particular value. When such a range is indicated, another aspect includes from a particular value and/or to other specific values. Similarly, when values are expressed as approximations, it is understood that the particular It will be further understood that the endpoints of each range are obviously related to the other endpoint and are not subject to the other endpoint.

Unless specifically stated to the contrary, the weight percent of a component is based on the total weight of the formulation or composition in which the component is incorporated.

The term "alkyl" as used herein is a branched or unbranched saturated hydrocarbon group of 1 to 40 carbon atoms, for example, methyl, ethyl, n-propyl, Isopropyl, n-butyl, iso-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, decyl or tetradecyl. The alkyl group can be substituted or unsubstituted. The term "unsubstituted alkyl" is defined herein as an alkyl group consisting solely of carbon and hydrogen. The term "substituted alkyl" is defined herein as an alkyl group having one or more hydrogen atoms substituted with a group including, but not limited to, aryl, cycloalkyl, aralkyl. Base, alkenyl, alkynyl, amine, ester, aldehyde, hydroxyl, alkoxy, thiol, sulfanyl or halide, sulfhydryl halide, acrylic or vinyl ether. For example, an alkyl group can be an alkyl hydroxy group in which any hydrogen atom of the alkyl group can be substituted with a hydroxy group.

As defined herein, the term "alkyl" also includes cycloalkyl. The term "cycloalkyl" as used herein is a ring composed of at least 3 carbon atoms based on a non-aromatic carbon. Examples of cycloalkyl groups include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and the like. The term cycloalkyl also includes heterocycloalkyl, wherein at least one carbon atom of the ring is substituted with a hetero atom such as, but not limited to, nitrogen, oxygen, sulfur or phosphorus.

The term "aryl" as used herein is any carbon-based aromatic group including, but not limited to, benzene, naphthalene, and the like. The term "aryl" also includes "heteroaryl", which is defined as an aryl group having at least one heteroatom incorporated into the ring of the aromatic group. Examples of heteroatoms include, but are not limited to, nitrogen, oxygen, sulfur, and phosphorus. The aryl group can be substituted or unsubstituted. An aryl group can be substituted with one or more groups including, but not limited to, alkyl, alkynyl, alkenyl, as defined herein. Aryl, halide, nitro, amine, ester, ketone, aldehyde, hydroxyl, carboxylic acid or alkoxy.

The term "aralkyl" as used herein is an aryl group having an alkyl group as defined above attached to an aryl group. An example of an aralkyl group is a benzyl group.

The term "alkenyl" is a branched or unbranched hydrocarbon group defined as 2 to 40 carbon atoms, and the structural formula contains at least one carbon-carbon double bond.

The term "alkynyl" is a branched or unbranched hydrocarbon group defined as 2 to 40 carbon atoms, and the structural formula contains at least one carbon-carbon reference.

The term "conjugated group" is a group defined as a linear, branched or cyclic group or a combination thereof, wherein the p-orbital domain of an atom within a group is linked via delocalization of electrons, and wherein the structure is It is described as comprising a replaceable single bond and a double bond or a reference bond, and may further comprise unshared electron pairs, free radicals or carbonium ions. The conjugated cyclic group may include aromatic and non-aromatic groups, and may include polycyclic or heterocyclic groups, for example, diketopyrrolopyrrole. Ideally, the conjugate group is bonded in such a manner as to conjugate between the thiophene molecular moieties that are attached to the conjugate group.

The present invention discloses compounds, compositions and ingredients that can be used in combination, useful in the preparation or as a product or composition of the disclosed methods. These and other materials are disclosed herein, and it should be understood that when a combination of such materials, sub-sets, interactions, groups, etc. are disclosed, the specific association of each individual individual and combination and arrangement of such compounds is not explicitly disclosed. Each of these is specifically covered and described herein. Therefore, if a class of molecules A, B, and C, and a class of molecules D, E, and F, and an example of a combination of molecules A-D are disclosed, In this case, even if each one is not individually quoted, each one is individually and collectively covered. Thus, in this example, each of the combinations AE, AF, BD, BE, BF, CD, CE, and CF are specifically covered and should be considered to expose A, B, and C; D, E, and F; And the combination example AD is disclosed. Likewise, any subset or combination of these is also specifically covered and disclosed. Thus, for example, subgroups of A-E, B-F, and C-E are specifically covered and should be considered to be disclosed from disclosures A, B, and C; D, E, and F; and combination examples A-D. This concept applies to all aspects of the disclosure, including but not limited to the steps in the method of making and using the disclosed compositions. Thus, if there are many additional steps that can be performed, it should be understood that each of these additional steps can be performed with any particular embodiment or combination of specific embodiments of the disclosed methods, and each Combinations are specifically covered and should be considered as disclosed.

In one aspect, disclosed herein is a composition comprising at least one molecular component of a cyclo-phenophene, the cyclopentene molecular moiety comprising Formula 3 or 4 : Or

In another aspect, the composition comprises at least one molecular moiety comprising Formula 3' or 4': Or

Wherein n is an integer greater than 0; m is not less than 1; in some embodiments, m is 2 or more; o is not less than 1; x is greater than or equal to 1; and R ₁ and R _{2 are} independently hydrogen. Or an alkyl group wherein at least one of R ₁ and R ₂ is an alkyl group, and Ar is an aryl group, wherein n is not 1.

In one aspect, with respect to structures 3, 3', 4 and 4' , n is an integer greater than 0; m is not less than 1; R ₁ and R _{2 are} independently hydrogen or alkyl, wherein at least one R ₁ and R ₂ is an alkyl group, and wherein n is not 1. As used herein, a cyclohexylthiophene ring system of a cyclopentene molecular moiety is a molecular moiety core of a heterocyclic ring and does not include an alpha-substituent and a beta-substituent (eg, R _{1 )} bonded to a cyclohexylthiophene ring system. And R ₂ ). For example, the structures 3 and 4 having a ring structure of n = 1 are shown in the following structures 5 and 6, respectively .

The cyclohexaphene molecule moieties described herein can have any number of bicyclic rings. For example, the cyclopentene molecular moiety can be bicyclic ( 3 and 3' , n = 1); tricyclic ( 4 and 4' , n = 1); tetracyclic ( 3 and 3' , n = 2) Five rings ( 4 and 4' , n=2); six rings ( 3 and 3' , n=3); or seven rings ( 4 and 4' , n=3). The methods described herein allow for the construction of a paracyclic thiophene molecule moiety having any desired number of rings. In one aspect, n is 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, or 15. In some embodiments, n is 2 or more. In other aspects, the cyclopentene molecular moiety can be tricyclic or more (i.e., 4 or 4' , n = 1; or 3 or 3' , n≧2). In some embodiments, the cyclopentene molecular moiety can be tetracyclic or more (ie, 4 or 4' , n≧2; or 3 or 3' , n≧2).

In another aspect, the composition includes at least one molecular moiety comprising Formula 3" or 4" :

Wherein n is an integer of 1 or more; m is an integer of 1 or more; X and Y are independently a covalent bond or an aryl group; and R ₁ and R _{2 are} independently an alkyl group, an olefin group, an alkyne group, or an aromatic group; Base, cycloalkyl, aralkyl, amine, ester, aldehyde, hydroxyl, alkoxy, thiol, thioalkyl, halide, sulfhydryl halide, acrylic acid or vinyl ether; R ₃ and R ₄ independently Is alkyl, olefin, alkynyl, aryl, cycloalkyl, aralkyl, amine, ester, aldehyde, hydroxy, alkoxy, thiol, thioalkyl, halide, sulfhydryl halide, acrylic acid Or vinyl ether; and A and B are independently S or O.

The paracyclic thiophene molecular moiety illustrated in 3" and 4" can have any number of comon rings in excess of 3. For example, the cyclopentene molecular moiety can be tetracyclic ( 3" , _n = 2); pentacyclic ( 4" , n = 2); six-ring ( 3" , n = 3); or seven-ring ( 4" , n=3). The methods described herein allow for the construction of a paracyclic thiophene molecule moiety having any desired number of rings. In one aspect, n is 1, 2, 3, 4 , 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, or 15 for 3" and 4" .

The cyclohexaphene moiety illustrated herein is substituted with an alkyl group at at least one β-position of the cyclohexylene ring system. As used herein, the α-position of the cyclo-thiophene ring system is the carbon center of the sulfur which is directly adjacent to the sulfur of the ring thiophene, and the β-position is the α-position of the sulfur with the cyclohexaphene. A non-coherent carbon center. In structures 3, 3', 3", 4, 4' and 4" , the α-position is shown by attachment to the remainder of the composition, while the β-position is replaced by R ₁ and R ₂ .

In one aspect, at least one of R ₁ and R ₂ is an alkyl group. Previously, there has been no method for producing a cyclopentene molecular moiety having an alkyl-substituted structure 3, 3', 3", 4, 4' and 4" at the β-position of the cyclophenophenone ring system. As explained in more detail in the examples below, the conventional methods for alkylating simple naphthene thiophenes are ineffective when used to attempt alkylation and cyclothiophene ring systems. In one aspect, described herein is a method of making a portion of a cyclo-thiophene molecule having a large number of alkyl substitutions at the β-position of the cyclophenophenone ring system.

In one aspect, R ₁ and R ₂ may be a variety of substituted or unsubstituted alkyl groups. For example, at least one R ₁ or R ₂ is an unsubstituted alkyl group. In this aspect, the unsubstituted alkyl group may be a linear alkyl group (for example, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, decyl, decyl, Undecyl, dodecyl or hexadecyl); branched alkyl (eg, second-butyl, neo-pentyl, 4-methylpentyl); or substituted or unsubstituted Cycloalkyl (eg, cyclopentyl, cyclohexyl). In another aspect, at least one R ₁ or R ₂ is a substituted alkyl group (which is itself at least four carbon atoms in size). In another aspect, the alkyl group is substituted with at least two carbon atoms from the cyclohexyl ring system. In one aspect, R ₁ and/or R ₂ may be aryl, cycloalkyl, aralkyl, alkenyl, alkynyl, amine, ester, aldehyde, hydroxy, alkoxy, thiol, Substituted by a sulfanyl group or a halide, a hydrazine halide, an acrylic acid or a vinyl ether. Examples of substituted alkyl groups include, but are not limited to, 6-hydroxyhexyl and 3-phenylbutyl. The choice of R ₁ and R ₂ will depend on the end use of the composition comprising the cyclopentene molecular moiety. The methods described herein allow for the synthesis of a cyclohexaphene molecule moiety having various ranges of R ₁ and R ₂ substituents. Any of the functions on the substituted alkyl group can be protected to survive in subsequent reaction steps.

The unsubstituted cyclo-thiophene ring system (i.e., unsubstituted at the α- or β-position) has a rather insoluble tendency. Thus, in one aspect, R ₁ and R ₂ may be an alkyl group having a size of at least six carbon atoms. For example, an alkyl group can have the formula C _k H _2k+1 , where k is an integer greater than or equal to 6.

In a particular aspect, the cyclohexyl ring system is substituted at two β-positions such that there is no β-hydrogen on the ring system. For example, in one aspect, in structures 3, 3', 3", 4, 4', and 4" , neither R ₁ nor R ₂ is hydrogen. Such molecular moieties can be incorporated into oligomers and polymers having substantially no beta-hydrogen content and will have increased oxidative stability. For example, the molar ratio of the beta-hydrogen to the cyclo-thiophene ring system can be less than about 1/6, 1/7, 1/8, 1/9 or 1/10. In another aspect, one or both of R ₁ and R ₂ may be an alkyl group. In one aspect, R ₁ and R ₂ are the same alkyl group. When R ₁ and R ₂ are the same, the stereoregular polymer can be easily constructed because the stereoselectivity (i.e., head-to-tail coupling to head-to-head coupling) of the polymerization reaction no longer exists. In other aspects, R ₁ and R ₂ may also be different. For example, R ₁ can be the size of at least four carbon atoms, while R ₂ is the size of less than four carbon atoms (eg, methyl). Alternatively, in another aspect, both R ₁ and R ₂ may be at least four carbon atoms in size.

With respect to the molecular moieties 3', 3", 4' and 4" , the aryl group (Ar) is attached to the α-position of the molecular portion of the cyclophenothiophene. The term "aryl" as used herein is any carbon-based aromatic. The aryl group may include a cyclo-aromatic, for example, naphthalene, onion, or the like. The term "aromatic" also includes "heteroaryl", which is defined as an aromatic having at least one heteroatom incorporated into an aromatic ring. Examples of heteroatoms include, but are not limited to, nitrogen, oxygen, sulfur, and phosphorus. The aryl group can be substituted or unsubstituted. An aryl group can be substituted with one or more groups including, but not limited to, alkyl, alkynyl, alkenyl, aryl, halide, nitro, amine, ester, ketone, aldehyde, hydroxy, carboxylic acid or Alkoxy.

In one aspect, wherein Ar comprises one or more acyclic cyclohexene groups, one or more cis-thiophene groups or a combination of a non-cyclic ring and a cyclo thiophene group. For example, the molecular portion includes Equation 200 or 201: Or

Wherein o is 1, 2 or 3, and R ₃ and R _{4 are} independently hydrogen or alkyl. In this aspect, Ar is one or more substituted or unsubstituted thiophene groups. In one aspect, n is 2, 3 or 4 and m is 1. In another aspect, n is 2, 3 or 4; m is 1; and o is 1, 2 or 3. When Ar is an example of a cyclohexylthiophene, it is contemplated that the cyclohexylthiophene may be a cyclohexylthiophene group or two or more cyclothiophene groups. When Ar is two or more cis-thiophene groups, the cis-thienyl groups may be the same or different. For example, Ar can be a bis-paracyclic thiophene covalently bonded to a tri-a-cyclothiophene. In other aspects, Ar can be one or more substituted or unsubstituted thiophene groups bonded to a substituted or unsubstituted cyclohexyl group.

In another aspect, there are molecular portions 3', 3", 4', and 4" , and the Ar molecular portion includes 300 or 301 :

Wherein A and B are O or S, and R ₃ and R _{4 are} independently substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, aryl, Cycloalkyl, aralkyl, amine, ester, aldehyde, hydroxyl, alkoxy, thiol, thioalkyl, halide, sulfhydryl halide, acrylic or vinyl ether, and X and Y are independently covalent Key or aryl. The term "aryl" as used in formulas 300 and 301 is any carbon-based aromatic. The aryl group may include a cyclo-aromatic group such as naphthalene, onion or the like. The term "aromatic" also includes "heteroaryl", which is defined as an aromatic having at least one heteroatom incorporated into the ring of the aromatic group. Examples of heteroatoms include, but are not limited to, nitrogen, oxygen, sulfur, and phosphorus. Ar may include one or more combinations of a non-cyclic thiophene group, one or more cis-thiophene groups or a non-cyclic ring and a cyclo thiophene group bonded dipyrrolopyrrole group. The aryl group can be substituted or unsubstituted. The aryl group may be substituted with one or more groups including, but not limited to, alkyl, alkynyl, alkenyl, aryl, halide, nitro, amine, ester, ketone, aldehyde, hydroxy , carboxylic acid or alkoxy.

The cyclopentadiene molecular moiety of structures 3, 3', 3", 4, 4' and 4" may be present as a simple monomeric cyclothiophene or may be incorporated into more complex compounds, oligomers or polymers in. For example, the paracyclic thiophene molecular moiety illustrated in 3 and 4 can be incorporated into a simple cyclo-thiophene monomer having formulas 7 and 8 :

Wherein n is an integer greater than 0; R ₁ and R _{2 are} independently hydrogen or alkyl; and Q is independently hydrogen, substituted or unsubstituted alkyl (eg, alkyl hydroxy), carboxylic acid, fluorenyl Halide, ester, aldehyde, ketone, hydroxyl, thiol or alkyl substituted thiol, alkoxy, acrylate, amine, vinyl ether or halide. In one aspect, each Q in 7 and 8 is bromine. In a particular aspect, monomers having structures 7 and 8 can be used in the manufacture of cyclophene oligopolymers and polymers, as described below.

The cyclo-thiophene monomers 7 and 8 can be incorporated into oligomers and polymers having a conjugated homooligomer or homopolymeric segment of the cyclopentene molecular moiety to produce a cyclopentene molecular moiety 3, 3 ', 3', 4, 4' and 4" polymers. For example, according to a particular embodiment, the oligomer or polymer comprises a cyclohexylthiophene of structures 3, 3', 3", 4, 4' and 4" , wherein m is greater than one. In other specific embodiments, m is at least about 4. In another specific embodiment, when the polymer is a homopolymer, m is at least about 10. In this aspect, it is contemplated that monomer 7 or 8 can be polymerized to produce a homopolymer consisting of residues having formula 3 or 4 . In other aspects, m is from 1 to 10,000, 1 to 9,000, 1 to 8,000, 1 to 7,000, 1 to 6,000, 1 to 5,000, 1 to 4,000, 1 to 3,000, 1 to 2,000, 1 to 1,000, 1 Up to 500, 1 to 250, 1 to 100, 1 to 50, 1 to 25 or 1 to 10.

In other aspects, the cyclohexaphene monomers (e.g., 7 and 8 ) described herein can be incorporated into a conjugated copolymer having other aromatic or unsaturated molecular moieties. For example, the cyclohexaphene monomers 7 and 8 can be partially copolymerized with other substituted or unsubstituted cyclo-thiophene molecules to form a conjugated cyclo-thiophene polymer or oligomer. Alternatively, the cyclohexaphene monomers 7 and 8 may also be copolymerized with a substituted or unsubstituted thiophene to form a thiophene/paracyclic thiophene polymer or oligomer. The cyclohexaphene monomers 7 and 8 can also be copolymerized with other molecular moieties of the polymer normally used for conjugation, for example, a vinyl group, a phenyl group or other aryl or heteroaryl group.

The cyclohexaphene molecule moieties described herein can be incorporated into a variety of other types of polymers. For example, a cyclo-thiophene having formulas 7 and 8 can be incorporated into the backbone of a polymer (eg, polyester, polyurethane, polyether, polyamine, polycarbonate, or polyketone); a side chain of a substance such as polyacrylate, polymethacrylate or poly(vinyl ether). It is contemplated that the cyclo-thiophene having formulas 7 and 8 can be modified with a reactive group (eg, mercapto chloride, ethanol, acrylic acid, amine, vinyl ether) which will allow for the incorporation of the monomer into the polymer. For example, R ₁ , R ₂ and/or Q may be modified by such reactive groups.

In other aspects, the molecular moieties 3', 3", 4', and 4" can be incorporated into a conjugated homooligomer or homopolymeric segment having 3', 3", 4', and 4" molecular moieties. In oligomers and polymers to make polymers. For example, according to a particular embodiment, the oligomer or polymer comprises a cyclohexylthiophene of structures 3, 3', 3", 4, 4' and 4" , wherein m is greater than one. In other specific embodiments, m is at least about 4. In another aspect, when the polymer is a homopolymer, m is at least about 10. In this aspect, it is contemplated that the molecular moieties 3', 3", 4', and 4" can be polymerized to produce a homopolymer. In other aspects, m is from 1 to 10,000, 1 to 9,000, 1 to 8,000, 1 to 7,000, 1 to 6,000, 1 to 5,000, 1 to 4,000, 1 to 3,000, 1 to 2,000, 1 to 1,000, 1 Up to 500, 1 to 250, 1 to 100, 1 to 50, 1 to 25 or 1 to 10.

In some embodiments, a conjugated homo-monomer (ie, a single), homo-oligo or homo-block polymer having 3', 3", 4', and 4" molecular moieties, having a molecular weight From about 10 Da to about 10,000 Da. In some embodiments, the molecular weight of the conjugated homo-monomer (ie, a single), homo-oligo or homo-blocked polymer having 3', 3", 4', and 4" molecular moieties, From about 10 Da to about 10,000 Da, about 100 Da to about 8000 Da, about 200 Da to about 7000 Da, about 300 Da to about 6000 Da, about 400 Da to about 5000 Da, about 500 Da to about 4000 Da, From about 500 Da to about 3000 Da, about 500 Da to about 2000 Da, about 500 Da to about 1500 Da, about 600 Da to about 1400 Da, about 700 Da to about 1300 Da, about 800 Da to about 1200 Da, about 900 Da to approximately 1100 Da or approximately 100 Da, 200 Da, 300 Da, 400 Da, 500 Da, 600 Da, 700 Da, 800 Da, 900 Da, 1000 Da, 1100 Da, 1200 Da, 1300 Da, 1400 Da, 1500 Molecular weights of Da, 1600 Da, 1700 Da, 1800 Da, 1900 Da, 2000 Da, 2500 Da, 3000 Da, 3500 Da, 4000 Da, 5000 Da, 6000 Da or 7000 Da.

In other aspects, the molecular moieties 3', 3", 4', and 4" can be incorporated into a conjugated copolymer having other aromatic or unsaturated molecular moieties. For example, the molecular moieties 3', 3", 4', and 4" can be partially copolymerized with other substituted or unsubstituted cyclo-thiophene molecules to form a conjugated cyclo-thiophene polymer or oligomer. Alternatively, the molecular moieties 3', 3", 4' and 4" may also be copolymerized with a substituted or unsubstituted thiophene to form a thiophene/paracyclic thiophene polymer or oligomer. The molecular moieties 3', 3", 4' and 4" may also be copolymerized with other molecular moieties of the polymers normally used for conjugation, for example, vinyl, phenyl or other aryl or heteroaryl groups. Molecular part.

The molecular moieties 3', 3", 4' and 4" described herein can be incorporated into various other types of polymers. For example, molecular moieties 3', 3", 4', and 4" can be incorporated into the backbone of a polymer (eg, polyester, polyurethane, polyether, polyamine, polycarbonate, or polyketone) a chain; and a side chain of a polymer (eg, polyacrylate, polymethacrylate, or poly(vinyl ether)). It is contemplated that the molecular moieties 3', 3", 4' and 4" may be modified with a reactive group (eg, mercapto chloride, ethanol, acrylic acid, amine, vinyl ether) which will allow the incorporation of the monomer into the polymer. in.

In one aspect, a compound comprising a molecular moiety 3' or 4' can be obtained by a compound comprising Formula 210 or 220 Or

(wherein n is an integer greater than or equal to 2; m is not less than 1; R ₁ and R _{2 are} independently hydrogen or alkyl, wherein at least one of R ₁ and R ₂ is alkyl), and has the formula (R ⁵ ) ₃ A compound of Sn-Ar-Sn(R ⁵ ) ₃ (wherein Ar includes an aryl group and R ⁵ is an alkyl group) is produced by reacting. In this aspect, the dibromocyclo thiophene is coupled to a bis-stannylaryl group. The coupling reaction is generally carried out in the presence of a catalyst (for example, Pd(0)). Figure 18 illustrates an aspect of this method in which dibromo-paracyclic thiophene (formula 210 , n = 3, m = 1) is with 2,5'-disienyltrimethyl-dithiophene, in Pd Coupling in the presence of (PPh ₃ ) ₄ to produce a copolymer. By this method, a copolymer such as a block copolymer can be produced in which the values of m and o in 3' and 4' can be changed depending on the molecular weight of the desired copolymer.

In another aspect, a compound comprising a molecular moiety 3" or 4" can be made by a series of synthetic steps. The cyclohexyl thiophene core can be synthesized and brominated as described herein. The dibromo-paracyclic thiophene can then be continuously reacted with butyllithium and trimethyltin chloride to form a bis-tin-substituted cyclothiophene as shown in FIG. The formation of the molecular moiety of the dipyrrolopyrrole can be accomplished by the reaction scheme shown by Tieke et al., Beilstein, J. Org. Chem. 830 (2010) (the entire contents of which are incorporated herein by reference) and In the figure, for example, the compound 3,6-bis(5-bromothien-2-yl)-2,5-di-heptadecylpyrrolo[3,4-c]pyrrole-1,4(2H,5H )-dione. The cyclophene molecule moiety and the dipyrrolopyrrole molecule moiety can be combined via any standard coupling reaction to form a 3" or 4" . In some aspects, the cyclohexaphene moiety and the dipyrrolopyrrole moiety can be combined via a Stille type coupling reaction as shown in Figure 22. The reaction in Fig. 22 uses a palladium (II) catalyst because palladium (II) catalyst exhibits excellent reliability, but a palladium (O = 0) based catalyst can also be used (for example, four (three) Phenylphosphine)palladium (0)).

In another aspect, a compound comprising molecular moiety 300 or 301 can be made by a series of synthetic steps. The cyclohexyl thiophene core can be synthesized and brominated as described herein. The dibromo-paracyclic thiophene can then be reacted with a palladium catalyst in the Stille type reaction in the presence of a tributylstannyl compound to give a polymer comprising an aryl group. Alternatively, the cyclohexaphene core can be continuously reacted with butyl lithium and trimethyltin chloride to form a bis-tin-substituted cyclothiophene, which can be followed by a brominated aryl molecule in a Stille type reaction. Partially reacted to form a conjugated polymer (Fig. 25). The reaction in Fig. 25 uses a palladium (0) catalyst because palladium (II) catalyst exhibits excellent reliability, but a palladium (II)-based catalyst can also be used.

In another aspect, the cyclophenothiens described herein can also be incorporated into a donor-acceptor chromophore, for example, a donor-acceptor chromophore commonly used to polymerize photovoltaic materials. For example, the paracyclic thiophene molecule moiety of structures 3 and 4 can be incorporated into a donor-acceptor chromophore having structure 9 or 10 :

Wherein D is an electron-donating group, and A is an electron-accepting group. </ RTI><RTIgt; In one aspect, a cyclo-thiophene having the formula 7 or 8 can be reacted with an electron-donating group and an electron-accepting group to produce a compound having the formulas 9 and 10 , respectively.

In various aspects, the compositions described herein have a sufficiently high concentration of a paracyclic thiophene molecule moiety of structure 3 or 4 to provide the desired electronic or optoelectronic properties for the composition. For example, the composition has a total concentration of at least 1% by weight of at least one structure 3 or 4 of a cyclo-thiophene molecule moiety. In another aspect, the compositions described herein have a total concentration of at least 3% by weight of at least one structure 3 or 4 of a cyclo-thiophene molecule moiety. In other aspects, the composition has a higher total concentration (eg, at least 10% by weight or at least 50% by weight) of at least one structural 3 or 4 cyclohexaphene moiety. Since an alkyl group is present at the β-position of the cyclophenothiophene ring, the composition may have a higher concentration of the cyclothiophene molecular moiety, but still maintain solubility and operability.

The compositions (monomers, oligomers, polymers) described herein can be used to make a variety of devices. For example, the device can be a composition comprising a cyclopentene molecular moiety disposed in an electronic, optoelectronic or nonlinear optical device. The compositions described herein can also be used in field effect transistors (FETs), thin film transistors (TFTs), organic light emitting diodes (OLEDs), PLED applications, photovoltaic (EO) applications, as conductor materials, as two-photon mixing. Materials, as organic semiconductors, as nonlinear optical (NLO) materials, as RFID tags, in electro-laser devices in flat panel displays, photovoltaic devices, and as chemical or biological sensors.

Polymers comprising the cyclopentene molecular moieties ( 3, 3', 3", 4, 4' and 4" ) described herein have enhanced packaging and thermal stability. The polymer also exhibits a liquid crystal phase that exceeds a specific temperature range. The liquid crystal properties can be easily converted by changing the length of the alkyl groups R ₁ and R ₂ . The polymer also has excellent solubility in organic solvents (e.g., THF, toluene, chlorobenzene), which allows for casting of the film using techniques known in the art.

Described herein are methods for making and cyclizing a thiophene compound. In one aspect, the method of making a β " -R-substituted cyclo-thiophene molecular moiety comprises the steps of: (i) providing an alpha-hydro-beta-bromothiophene molecular moiety; (ii) providing alpha-hydrogen-beta- The bromothiophene moiety is converted to α-(R-fluorenyl)-β- by deuterating the thiophene moiety at the α-position with an R-mercapto molecular moiety (wherein R is an alkyl group having at least 4 carbons). a molecular moiety of carboxymethylthiothiophene; (iii) a β-bromide substituted with 2-mercaptoacetic acid; (iv) a partial cyclization of the α-(R-fluorenyl)-β-carboxymethylthiothiophene molecule to form α "- carboxy -β" -R- and substituted thiophene ring molecular moiety; and (v) the α "- carboxy -β" -R- and substituted thiophene ring molecular moiety decarboxylation to form β "-R a substituted cyclo-thiophene molecular moiety.

In one aspect, the method of making a β " -R-substituted cyclo thiophene compound is shown in the reaction scheme of Figure 1. First, the alpha-hydro-β-bromothiophene molecular moiety 11 is provided. α-hydrogen-β The bromothiophene molecular moiety 11 can be a simple paracyclic thiophene as shown in the following structures 12 and 13. The structure 12 is an unsubstituted, paracyclic α-hydro-β-bromothiophene which has a single β after ring fusion. substituted thiophene and a thiophene structure 14 13 β 'center is R' substituted (i.e., a hydrogen alpha] -β- bromo -β '-R' - substituted thiophene)., after generating cyclic substituted fused double β- Thienothiophene 15 .

The α-hydro-β-bromothiophene molecule is then partially converted to the α-(R-fluorenyl)-β-carboxymethylthiothiophene molecular moiety 16 . The term "R-fluorenyl" as used herein refers to a radical structure 17 which is representative of the following, and the term "carboxymethylsulfide" refers to a radical structure 18 wherein Z is the end of the carboxylate group (may be For example, H, substituted alkyl, unsubstituted alkyl). In one aspect, Z is H, methyl, ethyl or propyl. The reaction scheme shown in Figure 2 and described in more detail in the examples can be used to achieve conversion of the α-hydro-β-bromothiophene molecular moiety 11 to α-(R-mercapto)-β-carboxymethylsulfide. Thiophene molecular moiety 16 . The α-hydro-β-bromothiophene molecular moiety is first thiolated at the α-position with an R-mercapto molecular moiety using RCOCl and AlCl ₃ , wherein R is an alkyl group having at least 4 carbon atoms. The thiolated product is reacted with 2-mercaptoacetic acid HSCH2COOZ to give the α-(R-indenyl)-β-carboxymethylthiothiophene molecular moiety 16 . Although the R-thiolation is carried out first in the reaction scheme of Fig. 2, in a specific example, the reactions can also be carried out in the reverse order.

The α-(R-fluorenyl)-β-carboxymethylthiothiophene molecular moiety 16 is then cyclized (eg, via a base-catalyzed condensation reaction, typically under the same conditions as the reaction with 2-mercaptoacetic acid). α " -carboxy-β " -R-substituted cyclo-thiophene molecular moiety 19 , which is partially decarboxylated to form a β " -R-substituted cyclothiophene molecular moiety 20 , wherein R is at least 4 carbons Alkyl.

If the α-hydro-β-bromothiophene molecular moiety 11 of the reaction scheme of Figure 2 has hydrogen at the α ' -position of the molecular moiety 11 of the α-hydro-β-bromothiophene, the thiolation step may be for the α-position. Not specific. For example, as shown in the reaction scheme of Figure 3, the α,α ' -dihydro-β-bromothiophene molecular moiety 21 is thiolated and reacted with 2-mercaptoacetic acid to form the desired α-(R-醯yl) -α '- [beta hydrogen carboxymethyl thiophene sulfur molecules and a bit portion 22 to the undesired isomeric α' - hydrogen -α- (R- acyl) [beta carboxymethyl thiophene sulfur molecular moiety A mixture of products of 23 . Since the molecular moieties 22 and 23 are likely to be separable from each other, a cyclization step on the mixture can be carried out; the isomer 22 will be cyclized to form α ' -hydro-α " -carboxy-β " -R - Substituted thiophene molecular moiety 24 , while the metameric isomer 23 will not be cyclized. And thiophene ring molecular moiety 24 can now be separated from the uncyclized position 23 to the isomers, and decarboxylation to afford α '- -R- substituted hydrogen -β "and thiophene ring 25 molecular moiety.

In another aspect, the methods illustrated in the reaction schemes of Figures 2 and 3 can be used to make various cyclo-thiophene compounds. For example, if the α-hydro-β-bromothiophene molecular moiety 11 of the reaction scheme of Figure 2 is the α-hydro-β-bromo-β ' -R ' -substituted thiophene molecular moiety 13 , then the final product is cyclothiophene. will be β "-R- substituted -β '-R' - substituted thiophene ring and molecular moiety 15 .R 'may be, for example, an alkyl group having at least 4 carbon atoms, and R may be the same or different and .R' It may also be any other desired substitution, including alkyl groups having less than 4 carbons.

The general cyclization process of the reaction scheme of Figure 2 can be used to simultaneously cyclize on both sides of the thiophene molecular moiety, as shown in the reaction scheme of Figure 4. The α,α ' -dihydro-β,β ' -dibromothiophene molecular moiety 26 is used as a starting material. Although the α,α ' -dihydro-β,β ' -dibromothiophene molecule moiety 26 is a simple thiophene which is shown as a single ring in the reaction scheme of Figure 4, it will be understood by those skilled in the art that the thiophene moiety 26 may have a fused-ring thiophene (e.g., thieno [3,2-b] thiophene or bis-thieno [3,2-b: 2 '-3 ' -d] thiophene) the thiophene molecule portion 26 and ring thiophene Ring system. Thiophene molecule portion 26 'is acyl of positions (e.g., above using Friedel-Crafts chemistry's), and beta] and beta]' in the [alpha] and [alpha] position with 2-mercapto acetic acid, to give α, α '- bis ( R- acyl) -β, β '- bis (carboxymethyl thio) thiophene molecule portion 27, the ring portion of the molecule (form 28) and decarboxylation to form β ", β''' - bis ( R-substituted) a cyclo-thiophene molecular moiety 29 having a two-ring cyclo-thiophene ring system larger than the starting thiophene molecular moiety 26. Alternatively, α,α ' -dihydro-β can also be used. The β ' -dibromothiophene molecular moiety 26 undergoes a first series of R-thiolation/reaction with 2-mercaptoacetic acid/cyclization/decarboxylation followed by a different R ' group in the thiolation step the second series of reactions, to provide a β "- (R- substituted) -β '''- (R ' - substituted) fused-ring thiophene molecular moiety, wherein R and R 'are different from each other.

The reaction scheme of Figure 5 shows another method for making the molecular moiety 27 of α,α ' -bis(R-fluorenyl)-β,β ' -bis(carboxymethylthio)thiophene. The α,α ' , β , β ' -tetrabromothiophene molecular moiety 30 is lithiated (optionally at the α-position) and reacted with the aldehyde RCHO to form the diol 31 , which oxidizes the diol to form α , α ' - bis(R-fluorenyl)-β,β ' -dibromothiophene moiety 32 , reacting the moiety with 2-mercaptoacetic acid to form α,α ' -bis(R-fluorenyl)- β,β ' -bis(carboxymethylthio)thiophene molecular moiety 27 .

The cyclopentadiene molecular moiety having a relatively large thiophene ring system can be synthesized by the above reaction scheme. A large paracyclic thiophene ring system can also be formed using the coupling and ring closure steps shown in the scheme of Figure 6. β-R- substituted -β '- bromothiophene molecular moiety 33 (wherein R is an alkyl group) is used as a raw material in this embodiment; synthesis route to 33 is described below. Although the β-R-substituted-β ' -bromothiophene molecule moiety 33 is shown to have a thieno[3,2-b]thiophene ring system in the reaction scheme of Figure 6, it may also have a single ring at the core. Thiophene, or a larger cyclo-thiophene ring system as described above. The β-R- substituted -β '- bromothiophene molecular moiety 33 lithiated, and reacted with bis (phenyl sulfonate) sulfur (or sulfur dichloride), 34 to form a thioether conjugate, thioether Lithiation and oxidation ring closure using CuCl ₂ to form a β,β " -disubstituted cyclothiophene molecular moiety 35 .

Polycyclic β-R- substituted -β '- bromo thiophene moiety can be by the β' - FIG. 2 for the first on-bromothiophene molecular moiety prepared a series of reactions as shown in Reaction Scheme 7 of FIG. Tetrabromothiophene is dilithiated (optionally at the a-position) and protonated to give dibromothiophene 37 , which is thiolated (obtained 38 ) and reacted with 2-mercaptoacetic acid to give α- (the R- acyl) [beta carboxymethyl sulfur -β '- bromothiophene molecular moiety 39, the ring portion of the molecule and decarboxylation to give 33. Although the starting material of the reaction scheme in Figure 7 is monocyclic thiophene, a polycyclic cyclo-thiophene starting material can also be used.

In another aspect, described herein is a β-R- substituted -β '- bromothiophene compounds, wherein R is alkyl as defined herein. For example, the compounds described herein include compounds having the structure 40 below. R may be, for example, an unsubstituted alkyl group.

According to this aspect, the unsubstituted alkyl group may be a linear alkyl group (for example, butyl, pentyl, hexyl, heptyl, octyl, decyl, decyl, undecyl, dodecyl or Cetyl); branched alkyl (eg, second-butyl, neo-pentyl, 4-methylpentyl); or substituted or unsubstituted cycloalkyl (eg, cyclopentyl, Cyclohexyl). In one aspect, R can be substituted or unsubstituted at least 7, at least 8, at least 9, at least 10 carbon-sized alkyl groups. In one aspect, the alkyl group is substituted by at least 2 carbons from the cyclohexyl ring system. According to this aspect, examples of the substituted alkyl group include 6-hydroxyhexyl group and 3-phenylbutyl group. The choice of the molecular moieties of R ₁ and R ₂ depends on the end use of the composition comprising the cyclopentene molecular moiety. Any of the functions on the substituted alkyl group can be protected to survive in subsequent reaction steps. Unsubstituted thiophene-based compositions have a relatively insoluble tendency; in this regard, in one aspect, R can be an alkyl group having at least six carbon sizes. For example, the alkyl group used to improve solubility includes C _k H _2k+1 , where k is an integer greater than or equal to 6.

In one aspect, the compound having the above structure 40 can be synthesized from the β-R-substituted thiophene molecule moiety by the bromination/debromination method shown in FIG. The β-R-substituted thiophene 41 is completely brominated with a bromine molecule to give a tribrominated compound 42 which is selectively lithiated and protonated at the α-position to give the desired β-R- substituted -β '- bromothiophene 40. The method of Figure 8 can also be used to make a portion of a β-brominated cyclothiophene molecule from a cyclopentene molecular moiety. The monocyclic β-R-substituted-β ' -bromothiophene 40 can be used to produce a tricyclic bis(R-substituted) cis-thiophene molecular moiety according to the reaction scheme shown in Figure 6. The monocyclic β-R-substituted-β ' -bromothiophene 40 can also be used to produce a monosubstituted cyclo thiophene molecular moiety according to the reaction scheme shown in Figure 9. For example, monocyclic thiophene 40 is lithiated and reacted with carbenyl piperidine, and the adduct is hydrolyzed to give aldehyde 43 which is reacted, cyclized, and decarboxylated with 2-mercaptoacetic acid to give β-R. - substituted cyclo thiophene 14 .

In one aspect, described herein is present in the thiophene ring, and any sulfur atom in the compound, can be oxidized to produce SO ₂ group. In another aspect, the composition comprises at least one of the following oxidized cyclothiophene molecular moieties:

In one aspect, with respect to structures 44 and 45 , n is an integer greater than 0; m is not less than 1; R ₁ and R _{2 are} independently hydrogen or alkyl, wherein each T is independently S or SO ₂ , wherein at least one T of the most central ring of the oxidized cyclo-thiophene ring system is SO ₂ , and wherein n is not 1 when the cyclohexaphene molecular moiety has the formula 45 . Each T is independently S or SO ₂ wherein at least one T of the most central ring of the cyclohexyl ring system is SO ₂ . As used herein, the most central ring of an odd-numbered 2q+1 cis-cyclic thiophene ring system is the q+1th ring from one end of the ring system. The most central ring having an even number of 2q ring-and-loop thiophene ring systems is the qth and q+1th rings from one end of the ring system. For example, the most central ring of the tricyclic system is the second ring, the most central ring of the four-ring system is the second and third rings, and the most central ring of the five-ring system is the third ring.

In another aspect, the oxidized molecular moiety comprises Formula 44' or 45' : Or

At least one T of the most central ring of the oxidized cyclo-thiophene ring system is SO ₂ . In one aspect, most of the at least one center ring T is SO _2, and S the remaining atoms are not oxidized.

Any of the oxidized cyclothiophene compounds described herein can be used in the polymers, oligomers, monomers, chromophores, and other compositions described above. For example, at least one oxidized cyclo-thiophene molecule moiety can be present in the composition in a total concentration of at least 1% by weight. The value of n can be, for example, 1, 2, 3, 4 or 5. In other aspects, the cyclopentene molecular moiety is tricyclic or larger (i.e., 45' , n≧1; or 44' , n≧1). In other aspects, at least one of R ₁ and R ₂ is an alkyl group of at least six carbon sizes directly bonded to the oxidized cyclo-thiophene ring system core of the oxidized and cyclized thiophene molecule moiety. Both R ₁ and R ₂ may be an alkyl group and may be the same or different from each other. In a particular aspect, neither R ₁ nor R ₂ is H. In other aspects, the composition has a ratio of less than about 1/10, 1/9, 1/8, 1/7, or 1/6 of the β-hydrogen to oxidized cyclo-thiophene ring system. In one aspect, the oxidized bicyclic compound has a structure:

Wherein n is an integer greater than 0; R ₁ and R _{2 are} independently hydrogen or alkyl; and Q is independently hydrogen, substituted or unsubstituted alkyl, fluorenyl halide, ester, aldehyde, ketone, hydroxy , thiol or alkyl substituted thiol, alkoxy, acrylate, amine, vinyl ether, hydroxyalkyl, carboxylic acid or halide.

The oxidized cyclohexyl thiophene compounds described herein can be incorporated into a cyclized thiophene polymer or oligomer having a conjugation of m > 1. Alternatively, the oxidized cyclothiophene compound can also be incorporated to include polyesters, polyurethanes, polyamines, polyketones, polyacrylates, polymethacrylates, polycarbonates, polyethers or A polymer of poly(vinyl ether). It is contemplated that when the polymer includes one or more molecular moieties 44' or 45', n can be greater than zero.

The oxidized cyclo-thiophene compounds and molecular moieties described herein can be prepared, for example, by oxidation with MCPBA. The most central ring oxidized in the polycyclic cyclo-thiophene ring system is generally selective; however, it is contemplated that any sulfur atom in the cyclohexylthiophene can be oxidized. Examples of oxidized cyclophenoxyl molecule moieties are shown in structures 46 , 47 , 48 and 49 below.

The cyclohexylthiophene and the oxidized cyclothiophene oligomer and the polymer can be prepared by a method similar to that described above for the production of oligo- and poly(thiophene). For example, the α,α ' -dihydrocyclo-thiophene molecular moiety can be oxidatively oligomerized or polymerized using an iron (III) compound (eg, FeCl ₃ , Fe(acac) ₃ ), or can be adjusted in organomagnesium. Bromination and coupling in the reaction. The cyclophene molecular moiety and the oxidized cyclothiophene molecular moiety described herein can be incorporated into other conjugated polymers using, for example, a phenyl group and an ethylene extending compound, which are familiar in the art. Base and acetylene copolymer. The cyclohexene molecular moiety and the oxidized cyclothiophene molecular moiety described herein can be incorporated into other backbone and side chain polymers using techniques known in the art. It is contemplated that the cyclohexaphene compound can be oxidized prior to incorporation into the oligomer or polymer. Alternatively, the cyclohexaphene compound can be incorporated into the oligomer or polymer after oxidation.

Example

The following examples are provided to provide a complete disclosure and description of the materials, articles, and methods described and claimed herein, and are not intended to limit the scope of the description. Efforts have been made to ensure the accuracy of the numbers (eg, amounts, temperatures, etc.), but some of the errors and deviations should be explained. Unless otherwise indicated, parts are parts by weight, temperature is °C or ambient temperature, and pressure is at or near atmospheric. There are many variations and combinations of reaction conditions, such as ingredient concentration, desired solvent, solvent mixture, temperature, pressure, and other reaction ranges, as well as conditions which can be used to optimize the purity and yield of the product obtained from the illustrated process. Only reasonable and routine experiments are required to optimize these process conditions.

Example 1: Di-β-substituted thieno[3,2-b]thiophene:

3,6-Dihexylthieno[3,2-b]thiophene 57 was synthesized as shown in the reaction scheme of Figure 10.

2,4,5-Tribromo-3-hexylthiophene ( 51 ). 3-hexylthiophene ( 50 ) (100 g, 0.595 mol) was mixed with 200 mL of acetic acid. Bromine (88 mL, 1.33 mol) was added dropwise to this mixture. After the addition of bromine, the resulting mixture was stirred at room temperature for 4 hours, heated at 60 ° C to 70 ° C overnight, then poured into 800 mL of ice water and neutralized with 6 M aqueous NaOH. The mixture was extracted with ethyl acetate (3×100 mL). The combined organic layers were washed with brine (2×100 mL) and water (100 mL) and dried over MgSO ₄ . The solvent was evaporated to give crude product 51 (234 g, 97.1% crude yield). This crude product is sufficiently pure for subsequent reactions. GC/MS: 404 g/mol (M-1). ^{_{1 H NMR (CD 2 Cl 2}} ): 2.64 (t, 2H), 1.51 (m, 2H), 1.32 (m, 6H), 0.89 (t, 3H). ¹³ C NMR: 143.69, 117.86, 111.48, 110.18, 33.62, 32.86, 30.96, 30.52, 24.70, 16.00.

3-bromo-4-hexylthiophene (52) . Compound 51 (70 g, 0.173 mol) was mixed with dry THF (400 mL). n-Butyllithium (138 mL, 2.5 M in hexane, 0.345 mol) was added dropwise to this mixture at -78 °C under argon. The resulting mixture was stirred for 10 minutes and then water (30 mL) was added to quench. The THF was evaporated and the EtOAc was evaporated. The combined organic layers in brine (2 × 100 mL), water (70 mL) washed, and dried over MgSO _4. After evaporating the solvent, the obtained crude product was purified by vacuum distillation (from 72 ° C to 74 ° C at 0.17 mbar) to afford 52 (35.3 g, 82.6% yield). GC/MS: 246 g/mol (M-1). ¹ H NMR (CD ₂ Cl ₂ ): 7.22 (s, 1H), 6.96 (s, 1H), 2.57 (t, 2H), 1.61 (m, 2H), 1.32 (m, 6H), 0.88 (t, 3H) ). ¹³ C NMR: 141.92, 122.87, 120.95, 112.89, 31.88, 30.07, 29.53, 29.20, 22.88, 14.14.

1-(3-Bromo-4-hexyl-2-thienyl)heptanone ( 53 ). To a mixture of compound 52 (24.7 g, 0.1 mol) and AlCl ₃ (26.8 g, 0.2 mol) in dry CH ₂ Cl ₂ (100 mL) was added dropwise at room temperature. . This mixture was stirred for 2 hours, after which GC/MS analysis showed the formation of the title compound 53 and the target compound 53 as the isomer 1-(4-bromo-3-hexyl-2-thienyl)heptanone ( 54 ) A 3:1 mixture. The reaction mixture was poured into 200 mL of 6 M HCl and washed with water (3×50 mL). The organic layer was dried on MgSO _4; and the solvent was evaporated to give a crude mixture of compound 53 and 34.7 g of 54, and the crude mixture was used for the next reaction without isolation or further purification.

3,6-Dihexylthieno[3,2-b]thiophene-2-carboxylic acid ( 55 ). A mixture of compounds 53 and 54 (66.5 g, 0.185 mol) was mixed with K ₂ CO ₃ (53.6 g, 0.39 mol) and a catalytic amount of 18-crown-6 in 200 mL DMF. Ethyl 2-mercaptoacetate (20.3 mL, 0.185 mol) was added dropwise to this mixture at 60 ° C to 70 ° C. The reaction mixture was stirred overnight at 60 ° C to 70 ° C and then poured into water (800 mL). The organic extracts were extracted with ethyl acetate (3×100 mL) and combined organic extracts washed with brine (2×100 mL) and water (100 mL). The solvent was removed by evaporation, and the residue was dissolved in THF (300 mL) to form a solution, then LiOH (84 mL, 10% solution in water), MeOH (50 mL) and catalytic iodination Tetrabutylammonium. The mixture was heated at reflux for 3 h then the solvent was evaporated and evaporated and evaporated. After diluting with 200 mL of water, the organics were extracted with ethyl acetate (3×100 mL). The combined organic layers in brine (2 × 100 mL), water (100 mL) washed, and dried over MgSO _4. After the solvent was evaporated, the column was chromatographed (SiO ₂ / 5% ethyl acetate in hexane with 20% ethyl acetate in hexane to completely elute compound 55 ), and compound 55 was unreacted. Compound 54 was isolated to afford pure compound 55 (30 g, 46.1% yield). ¹ H NMR (CD ₂ Cl ₂ ): 7.24 (s, 1H), 3.18 (t, 2H), 2.73 (t, 2H), 1.75 (m, 4H), 1.34 (m, 14H), 0.89 (m, 6H) ). ¹³ C NMR: 169.15, 146.25, 143.10, 141.49, 136.14, 126.67, 126.11, 31.99, 29.74 (6C), 22.99, 14.24.

3,6-Dihexylthieno[3,2-b]thiophene ( 57 ). A mixture of compound 55 (30 g, 0.085 mol), copper powder (3.76 g) and quinoline (80 mL) was heated in a Woods metal bath at 264 ° C to 260 ° C. When no further carbon dioxide bubbles were detected (about 2 hours), the mixture was allowed to cool to room temperature and hexane (200 mL) was added. This mixture was repeatedly washed with HCl (1-2 M in water) to remove quinoline. The remaining organic layer was dried over MgSO _4, and concentrated by evaporation, leaving a residue, the residue was purified by column chromatography (SiO ₂ / hexane) to afford compound 57 (18 g, 68.4%). Melting point 57.5 ° C to 59.1 ° C, ¹ H NMR (CD 2 Cl 2 ): 6.97 (s, 2H), 2.70 (t, 4H), 1.73 (m, 4H), 1.37 (m, 12H), 0.88 (t, 6H). ¹³ C NMR: 136.56, 134.96, 109.80, 31.94, 29.31, 29.28, 28.47, 22.96, 14.22. The same reaction sequence was used to produce 3,6-dimercaptothieno[3,2-b]thiophene ( 58 ).

Example 2: Mono-β-substituted thieno[3,2-b]thiophene.

3-hexylthieno[3,2-b]thiophene 58 was synthesized as shown in the reaction scheme of Figure 11.

1-(3-Bromothienyl)heptanone ( 59 ). To a solution of 3-bromothiophene ( 60 ) (16.3 g, 0.1 mol), AlCl ₃ (26.8 g, 0.2 mol) and CH ₂ Cl ₂ (100), was added dropwise at room temperature to heptane chloride (14.9 g, 0.1 mol). In a mixture of mL). The resulting mixture was stirred for 2 hours before GC/MS showed compound 60 was completely converted to compound 59 . The reaction mixture was poured into cold HCl (6M, 200 mL). The organic component was extracted with hexane (3 x 100 mL). The combined organic layers were washed with brine (2 x 100 mL) and water (100 mL). After dried over MgSO _4, the crude target compound was purified by column chromatography (SiO ₂ / hexane) to give compound 59 (25.1 g, 91.3% yield). GC/MS: 275 g/mol (M). ¹ H NMR (CD ₂ Cl ₂ ): 7.53 (d, 1H), 7.12 (d, 1H), 3.01 (t, 2H), 1.71 (m, 2H), 1.38 (m, 6H), 0.92 (t, 3H) ).

Ethyl 3-hexylthieno[3,2-b]thiophene-2-carboxylate ( 61 ). Compound 59 (35.4 g, 0.13 mol) and K ₂ CO ₃ (27.6 g, 0.2 mol) were combined with N,N-dimethylformamide (100 mL). A catalytic amount (about 25 mg) of 18-crown-6 was added, and ethyl 2-mercaptoacetate (14.0 mL, 0.13 mol) was added dropwise to this mixture at 60 °C. The mixture was stirred overnight and poured into water (500 mL). The organic component was extracted with ethyl acetate (3×80 mL). The combined organic layers were washed with brine (2 x 100 mL) and water (100 mL). Then the organic layer was dried on MgSO _4. After evaporating the solvent, crude compound 61 was obtained and purified by column chromatography (SiO ₂ / 5% ethyl acetate in hexane) to afford pure compound 61 (32.1 g, 84.5%). GC/MS: 296 g/mol (M). ¹ H NMR (CD ₂ Cl ₂ ): 7.56 (d, 1H), 7.24 (d, 1H), 4.34 (q, 2H), 3.15 (t, 2H), 1.71 (m, 2H), 1.32 (m, 6H) ), 0.88 (m, 6H). ¹³ C NMR: 163.24, 143.31, 141.85, 141.09, 131.13, 128.44, 120.35, 61.25, 31.99, 29.72 (overlap), 22.98, 14.52, 14.23.

3-hexylthieno[3,2-b]thiophene-2-carboxylic acid ( 62 ). Compound 61 (32.1 g, 0.11 mol) with LiOH (10% in water, 50 mL), THF (100 mL), MeOH (30 mL) and a catalytic amount (about 20 mg) of tetrabutylammonium iodide Mix in a 500 mL Erlenmeyer flask. This mixture was heated overnight under reflux and the mixture was cooled to room temperature and acidified with concentrated EtOAc. The resulting yellow solid was collected by filtration and washed thoroughly with water. The solid was then heated in hexanes (100 mL) and the solid was cooled to room temperature. After filtration, the solid was collected and dried in vacuo to give compound 62 as pale yellow powder (28.0 g, 96.7%). Melting point: 110.7 ° C to 112.4 ° C.

3-hexylthieno[3,2-b]thiophene ( 58 ). A mixture of compound 62 (14.6 g, 0.054 mol), copper powder (2.00 g) and quinoline (80 mL) was heated at 260 ° C in a wood metal bath. When no further carbon dioxide bubbles were detected (about 2 hours), the mixture was allowed to cool to room temperature and hexane (200 mL) was added. The mixture was washed repeatedly with HCl (1-2 M in water) to remove quinoline. The organic layer was concentrated by evaporation and dried over MgSO _4, and. The residue was purified by column chromatography (SiO ₂ /hexane) to afford compound 58 (25.1 g, 90.3%). GC/MS: 224 g/mol (M). ¹ H NMR (CD ₂ Cl ₂ ): 7.36 (m, 1H), 7.25 (m, 1H), 7.01 (m, 1H), 2.73 (t, 2H), 1.69 (m, 2H), 1.34 (m, 6H) ), 0.89 (t, 3H). ¹³ C NMR: 140.39, 139.13, 135.39, 127.01, 122.19, 120.26, 32.01, 30.29, 29.43, 23.01, 14.24.

Example 3: two -β- di-substituted thieno [3,2-b: 2 '-3 ' -d] thiophene And di-β-substituted dithieno[3,2-b:2 ' -3 ' -d]thiophene-4,4-dioxide.

Synthesis of 3,6-dimercaptothieno[3,2-b]thiophene 63 and 3,6-dimercaptothieno[3,2-b]thiophene-4 as shown in the scheme of Figure 12, 4-dioxide 64 .

1,1 ' -(3,4-Bromo-2,5-thienyl)di-undecyl alcohol ( 65 ). Butyllithium (160 mL, 0.4 mol, 2.5 M in hexane) was added dropwise to a solution of tetrabromothiophene 36 (80.0 g, 0.2 mol) and THF (500 mL) at -78 °C. Undecyl aldehyde (DecCHO) (69.7 g, 0.41 mol) was added, and the reaction mixture was stirred for 2 hr. The THF solvent was then removed by evaporation and the organic residue was extracted with hexane. The combined organic layers in brine (2 × 100 mL) and water (100 mL) washing, drying over MgSO _4. The crude product was purified by column chromatography (SiO _2/5% ethyl acetate in hexanes) and purification to give Compound 65 (84.1 g, 72.5% yield). ¹ H NMR (CD ₂ Cl ₂ ): 5.02 (broad, 2H), 1.79 (m, 4H), 1.28 (m, 32H), 0.88 (t, 6H). ¹³ C NMR: 143.25, 109.67, 70.53, 38.31, 31.96, 29.75, 29.70, 29.61, 29.55, 29.21, 25.68, 22.84, 14.09.

1,1 ' -(3,4-Bromo-2,5-thienyl)di-undecenone ( 66 ). A chromic acid solution was prepared by dissolving 100 g of sodium dichromate dihydrate (0.34 mol) in water (300 mL), then 136 g of concentrated sulfuric acid was added, and the resulting solution was diluted to 500 mL. Compound 65 (80.0 g, 0.137 mol) was mixed with acetone (300 mL). A chromic acid solution (260 mL) was added dropwise to this mixture at room temperature. The mixture was stirred overnight, after which a large amount of solid was formed in the reaction mixture. Most of the acetone was transferred to the other vessel and the remaining mixture was extracted with ethyl acetate (2×100 mL). The combined organic layers in brine (3 × 50 mL) washed, and dried over MgSO _4. The solvent was evaporated, and the residue was mixed with ethanol (100 mL) were mixed white and pure compound 66 solidified and was collected by filtration (72.0 g, 90.5% yield). Melting point: 69.5 ° C to 70.8 ° C. ¹ H NMR (CD ₂ Cl ₂ ): 3.07 (t, 4H), 1.74 (m, 4H), 1.28 (m, 28H), 0.88 (t, 6H). ¹³ C NMR: 192.49, 141.99, 118.82, 42.03, 32.13, 29.79, 29.71, 29.62, 29.55, 29.29, 24.16, 22.92, 14.11.

3,5-Dimercaptodithieno[3,2-b:2 ' , 3'- d]thiophene-2,6-dicarboxylic acid diethyl ester ( 67 ). Compound 66 (30.0 g, 0.052 mol) was combined with K ₂ CO ₃ (28.7 g, 0.21 mol) and N,N-dimethylformamide (100 mL). Ethyl 2-mercaptoacetate (11.5 mL, 0.104 mol) was added dropwise to this mixture at 60 °C. The reaction mixture was stirred at 60 ° C under nitrogen for 48 hours then poured into water (500 mL). The organic component was extracted with ethyl acetate (3×100 mL). The combined organic layers in brine (2 × 100 mL) and water (50 mL) washed, and dried over MgSO _4. The solvent was evaporated and the residue was purified by column chromatography (SiO _2/5% ethyl acetate in hexanes) and purification to give compound 67 as a viscous, low melting solid (19.1 g, 59.3% yield rate). ¹ H NMR (CD ₂ Cl ₂ ): 4.36 (q. 4H), 3.15 (t, 4H), 1.73 (m, 4H), 1.39 (m, 36H), 0.87 (m, 6H). ¹³ C NMR: 162.86, 145.47, 144.51, 133.05, 128.99, 61.63, 32.33, 29.99 (overlap), 23.11, 14.53, 14.31.

3,5-Dimercaptodithieno[3,2-b:2 ' , 3'- d]thiophene-2,6-dicarboxylic acid ( 68 ). Compound 67 (10.2 g, 0.017 mol) was mixed with LiOH (1.0 g in 10 mL of water), THF (100 mL), MeOH (20 mL) and a catalytic amount (about 35 mg) of tetrabutylammonium iodide. This mixture was heated at reflux overnight and then most of the solvent was evaporated. The residue was treated with concentrated HCl (30 mL) and acidified to form a solid, and the solid was collected by filtration, washed thoroughly with water and dried in vacuo to give compound 68 (8.6 g, 98% yield). Melting point: 280.1 ° C. ¹ H NMR (CD ₂ Cl ₂ ): 3.24 (t, 4H), 1.72 (m, 2H), 1.29 (m, 30H), 0.88 (t, 6H). ¹³ C NMR: 168.46, 148.24, 146.58, 136.32, 35.91, 33.64, 28.91 (m, overlap), 26.60, 17.49.

3,5-Dimercaptodithieno[3,2-b:2 ' , 3'- d]thiophene ( 63 ). Compound 68 (8.6 g, 0.016 mol), copper powder (0.7 g) and quinoline (50 mL) were combined and heated in a wood metal bath at 250 ° C to 260 ° C. When no further carbon dioxide bubbles were detected (about 2 hours), the mixture was cooled to room temperature and hexane (200 mL) was added. This mixture was washed repeatedly with HCl (1-2 M in water) to remove quinoline. The organic layer was concentrated by evaporation and dried over MgSO _4, and and the residue was purified by column chromatography (SiO ₂ / hexanes) and purification to give compound 63 (3.4 g, 47.4%) . ¹ H NMR (CD ₂ Cl ₂ ): 6.97 (s, 2H), 2.73 (t, 4H), 1.78 (m, 4H), 1.27 (m, 28H), 0.88 (t, 6H). ¹³ C NMR: 148.99, 136.75, 130.99, 120.57, 32.33, 30.02, 29.79 (m, overlap), 29.74, 29.15, 23.10, 14.28.

Compounds 64 and 69 are those of Sogiu et al. "Hard core fluoro oligothiophene-S, S-dioxide isothiocyanate: synthesis, optical properties and conjugation to monoclonal antibodies" (J. Org. Chem.). It is prepared by the method described in 2003, 68, 1512-1520, which is incorporated herein by reference.

3,5-Dimercaptodithieno[3,2-b:2 ' , 3'- d]thiophene-4,4-dioxide ( 64 ). To a solution of 63 (3.64 g, 8.18 mmol) in 20 mL of dichloromethane was added dropwise to a solution of 3-chloroperoxybenzoic acid (6.1 g, 0.035 mol) in 20 mL of CH ₂ Cl ₂ . The mixture was stirred at room temperature overnight, then 10% KOH, 10% NaHCO ₃ and brine continuous cleaning. The organic layer was dried over Mg ₂ SO ₄ and the solvent was removed by evaporation. The crude product was purified by column chromatography (SiO _2/5% ethyl acetate in hexanes) and purification to give compound 64 as a yellow solid (1.4 g, 35.9% yield). Melting point: 58.7-60.3 °C. ¹ H NMR (CD ₂ Cl ₂ ): 6.94 (s, 2H), 2.73 (t, 4H), 1.72 (m, 4H), 1.27 (m, 28H), 0.88 (t, 6H). ¹³ C NMR: 142.99, 139.06, 136.36, 124.51, 32.27, 30.11, 29.95, 29.91, 29.68, 29.48, 29.51, 28.51, 23.04, 14.22.

3,5-Dimercaptodithieno[3,2-b:2 ' , 3'- d]thiophene-4,4-dioxide-2,6-dicarboxylic acid diethyl ester ( 69 ). The 20 mL of CH ₂ Cl ₂ in the 3-chloroperoxybenzoic acid (1.2 g, 6.9 mmol), added dropwise to 67 (3.64 g, 8.18 mmol) solution in 20 mL of methylene chloride. The mixture was stirred at room temperature overnight, then 10% KOH, 10% NaHCO ₃ and brine continuous cleaning. The organic layer was dried over Mg ₂ SO ₄ and the solvent was removed by evaporation. The crude product was purified by column chromatography (SiO _2/5% ethyl acetate in hexanes) and purification to give compound 69 as a waxy solid (0.56 g, 53% yield). ¹ H NMR (CD ₂ Cl ₂ ): 4.39 (q, 4H), 3.13 (t, 4H), 1.72 (m, 4H), 1.27 (m, 34H), 0.88 (t, 6H). ¹³ C NMR: 161.41, 145.52, 144.77, 137.56, 132.89, 62.03, 32.11, 30.59, 29.82, 29.78, 29.75, 29.53, 29.49, 27.88, 22.89, 14.21, 14.07.

The reaction scheme of Figure 12 is also used to produce 3,5-dihexyldithieno[3,2-b:2 ' , 3'- d]thiophene and 3,5-dihexyldithieno[3,2- b: 2 ' , 3 ' -d] thiophene-4,4-dioxide.

Example 4: Di-β-substituted thieno[3,2-b]thieno[2 ' ,3 ' :4,5]thieno[2,3-d]thiophene.

3,7-Dimercaptothieno[3,2-b]thieno[2 ' ,3 ' :4,5]thieno[2,3-d]thiophene 70 is as shown in the scheme of Figure 13 And synthesis.

2,4-Di(1-hydroxyindenyl)-3,6-dibromothieno[3,2-b]thiophene ( 72 ). 2,3,4,5-tetrabromothieno[3,2-b]thiophene ( 71 ) is prepared according to Fuller et al, J. Chem. Soc., Perkin Trans, 1, 1997, 3465, which is The citation is included in this article. Butyllithium (70 mL, 0.175 mol, 2.5 M in hexane) was added dropwise at -78 °C to a mixture of compound 71 (40.0 g, 0.088 mol) in 300 mL anhydrous THF. The resulting mixture was stirred for another 10 to 20 minutes, and undecylaldehyde (30.0 g, 0.176 mol) was added dropwise. The mixture was allowed to warm to room temperature and stirred overnight. Water (20 mL) was added and the solvent was removed by evaporation. The residue was mixed with hexane (300 mL) and the obtained solid was collected by filtration. This solid was then dried under vacuum to give compound 72 (47.0 g, 83.9% yield). Melting point: 116.0-118.0 °C. ¹ H NMR (CD ₂ Cl ₂ ): 5.15 (m, 2H), 2.31 (b,, 2H), 1.91 (m, 4H), 1.31 (m, 32H), 0.92 (t, 6H). ¹³ C NMR: 144.06, 109.05, 70.58, 38.77, 32.36, 30.06, 30.04, 29.99, 29.77, 29.65, 26.09, 23.12, 14.29.

2,4-Di-undecylfluorenyl-3,6-dibromothieno[3,2-b]thiophene ( 73 ). Compound 72 (30.0 g, 0.047 mol) was mixed with acetone (200 mL). A chromic acid solution (130 mL) was added dropwise to this mixture at room temperature. The mixture was stirred overnight at room temperature, after which a large amount of solid was formed in the reaction mixture. Most of the acetone was transferred to the other vessel and the remaining mixture was extracted with ethyl acetate (2×100 mL). The combined organic layers in brine (3 × 50 mL) washed, and dried over MgSO _4. The solvent was evaporated, and the residue was mixed with ethanol (100 mL) were mixed white and pure compound 73 (18.4 g, 61.7% yield) curing, and collected by filtration. Melting point: 120.3 ° C to 121.5 ° C. ¹ H NMR (CD ₂ Cl ₂ ): 3.09 (t, 4H), 1.78 (m, 4H), 1.28 (m, 28H), 0.88 (t, 6H). ¹³ C NMR: 193.15, 143.62, 143.40, 106.70, 41.74, 32.12, 29.79, 29.72, 29.65, 29.55, 29.35, 24.20, 22.91, 14.11.

3,7-diamidylthieno[3,2-b]thieno[2',3':4,5]thieno[2,3-d]thiophene-2,6-dicarboxylic acid diethyl ester ( 74 ). Compound 73 was mixed with K ₂ CO ₃ (16.6 g, 0.12 mol) and N,N-dimethylformamide (100 mL). 2-Mercaptoacetate (6.6 mL, 0.06 mol) was added dropwise to this mixture at 60 °C. The reaction mixture was stirred at 60 ° C for 48 hours under nitrogen then poured into water (500 mL). The resulting solid was collected by filtration. The crude product was then boiled with ethanol (200 mL) and cooled to room temperature. Filtration and drying gave Compound 74 (14.2 g, 72.4% yield). Melting point: 130.5 ° C to 132.2 ° C. ¹ H NMR (CD ₂ Cl ₂ ): 4.36 (q. 4H), 3.15 (t, 4H), 1.73 (m, 4H), 1.27 (m, 34H), 0.87 (m, 6H). ¹³ C NMR: 163.09, 144.79, 144.29, 135.29, 134.28, 128.54, 61.83, 32.57, 30.32, 30.26, 30.21, 30.07, 30.02, 29.98, 29.79, 23.33, 14.79, 14.49.

3,7-diamidinothieno[3,2-b]thieno[2',3':4,5]thieno[2,3-d]thiophene-2,6-dicarboxylic acid ( 75 ) . Compound 74 (14.0 g, 0.021 mol) was mixed with LiOH (1.24 g in 15 mL water), THF (100 mL), MeOH (20 mL) and a catalytic amount of tetrabutylammonium iodide. This mixture was heated at reflux overnight and then most of the solvent was evaporated. The residue was acidified with cone. HCl (30 mL). The obtained solid was collected by filtration, washed thoroughly with water and dried in vacuo to afford compound 75 (12.5 g, 97.4% yield). Melting point: 315.6 ° C to 318.5 ° C.

3,7-Dimercaptothieno[3,2-b]thieno[2',3':4,5]thieno[2,3-d]thiophene ( 70 ). Compound 75 (13.5 g, 0.021 mol) was mixed with copper powder (0.9 g) in quinoline (80 mL), and the mixture was heated to 250 ° C to 260 ° C in a wood metal bath. When no further carbon dioxide bubbles were detected (about 2 hours), the mixture was allowed to cool to room temperature and hot hexane (400 mL) was added. This mixture was washed repeatedly with HCl (2N, 4×50 mL). The hexane was partially removed by evaporation, and the obtained solid was collected by filtration and recrystallized from hexane to give compound 70 (7.0 g, 60.6% yield). Melting point: 111.0 ° C to 113.3 ° C. ¹ H NMR (C ₆ D ₆ ): 6.53 (s, 2H), 2.51 (t, 4H), 1.64 (m, 4H), 1.27 (m, 28H), 0.89 (t, 6H). ¹³ C NMR: 141.26, 136.42, 133.17, 132.04, 120.73, 32.31, 30.03, 29.96, 29.90, 29.79, 29.66, 29.04, 23.07, 14.28.

Example 5: The synthesis of β-substituted thieno[2,3-d]thiophenes could not be attempted using conventional coupling reactions.

The reaction scheme of Figure 14 was followed by an unsuccessful attempt to synthesize a β-hexyl-substituted thieno[2,3-d]thiophene. Since the electronic properties of the ring system are far different from the electronic properties of simple monocyclic thiophenes, the coupling reaction for monocyclic thiophenes does not work.

Dissolve 3,6-dibromothieno[3,2-b]thiophene ( 76 , 5.2 g, 0.0175 mol) in anhydrous diethyl ether (100 mL) with [1,3-bis(diphenyl) Phosphyl)propane]di-chloronickel(II) (dppp) (0.47 g, 0.05 equivalent) was mixed. Hexylmagnesium bromide (22.0 mL of a 2.0 M solution in diethyl ether, 0.044 mol) was added dropwise to this solution. The resulting mixture was heated under reflux for 24 hours. The reaction was monitored by GC/MS. After 24 hours, the starting material disappeared but no Grignard addition product was formed.

Dissolve 3-bromo-6-hexylthieno[3,2-b]thiophene ( 77 , 6.2 g, 0.021 mol) in anhydrous diethyl ether (100 mL) with [1,3-bis(diphenyl) Alkylphosphino)propane]di-chloronickel(II) (dppp) (0.51 g, 0.05 equivalent) was mixed. Hexylmagnesium bromide (13.3 mL of a 2.0 M solution in diethyl ether, 0.027 mol) was added dropwise to this solution.

The resulting mixture was heated under reflux for 24 hours. The reaction was monitored by GC/MS. After 6 hours, the raw materials disappeared but did not form Gerry. Nagarate product.

Example 6: Poly(β-substituted cyclothiophene)

The cyclohexyl thiophene polymer is prepared by the general procedure described below. This method is adapted from Andersson et al. (Macromolecules 1994, 27, 6506), which is incorporated herein by reference.

The monomeric α,α ' -dihydro-β,β ' -dialkylcyclo thiophene compound (10 mmol) was dissolved in 30 mL of chlorobenzene. A suspension of ferric chloride (2.5 mmol) in 20 mL of chlorobenzene was added to the monomer solution for more than half an hour. The mixture is stirred at room temperature for a number of (e.g., 6 to 24) hours. It is desirable to heat the reaction mixture at 80 ° C to 90 ° C for several hours for a larger (e.g., 4 or greater) number of ring-and-cyclic thiophene compounds in the cis ring system of the cyclized thiophene compound. The reaction mixture was then precipitated from 500 mL of 95:5 methanol:water. The precipitate was collected by filtration, dissolved in toluene, boiled with concentrated aqueous ammonia (3×60 mL), and boiled with ethylenediaminetetraacetic acid (0.05 M in water, 2×50 mL). The organic layer was precipitated from methanol (500 mL), filtered and dried in vacuo (70 ° C to 80 ° C).

Preparation of poly(3,6-dihexylthieno[2,3-d]thiophene) (35% yield); poly(3,6-dimercaptothieno[2,3-d]thiophene (90% yield) Rate); poly(3,7-dimercaptothieno[3,2-b]thieno[2 ' ,3 ' :4,5]thieno[2,3-d]thiophene) (80% yield) And poly(3,5-dimercaptodithieno[3,2-b:2 ' , 3'- d]thiophene-4,4-dioxide) (43% yield).

Example 7: Synthesis of 2-, 3-3 and 4-4 dimers and 5 and 7 ring systems.

The synthesis of the 2, 2, 3-3 and 4-4 dimers and the 5 and 7 ring systems is illustrated in Figure 15.

3,3'-Dibromo-6,6'-dimercapto-2,2'-bisthienothiophene ( 82 ). Butyllithium (2.5 M in hexane, 15.6 mL, 0.039 mol) was added dropwise at 0 °C to a cone of diisopropylamine (4.0 g, 0.039 mol) in anhydrous THF (30 mL) bottle. The resulting mixture was kept at 0 ° C for 15 minutes. 3-Bromo-6-mercaptothiophenethiophene ( 81 ) (14.0 g, 0.039 mol) was added dropwise in THF (30 mL). The mixture was stirred at 0 ° C for 1 hour, and then copper (II) chloride (6.3 g, 0.047 mol) was added. This dark brown solution was stirred at room temperature for a further 12 hours. After evaporating all the solvent, the residue was boiled with toluene (200 mL) and filtered. The organic solution was concentrated with brine (2 × 50 mL), water (50 mL) washed, and dried over MgSO _4. After evaporating the toluene, the residue was boiled with ethanol (700 mL) and the solid was collected after cooling. The title compound was collected as a yellow solid crystalline powder. This gave 9.35 g (67%). Melting point: 90.0 ° C to 91.0 ° C. ¹ H NMR: solvent CD ₂ Cl ₂ . ¹ H NMR: 7.15 (s, 2H), 2.74 (t, 4H), 1.89-1.27 (m, 32 H), 0.89 (t, 6H). ¹³ C NMR: 140.78, 136.25, 133.02, 131.65, 131.23, 120.47, 31.92, 29.61 (overlapping), 29.36 (overlapping), 28.73, 22.69, 14.11.

3,6-Dimercapto-dithieno[2,3-d:2',3'-d']thieno[3,2-b:4,5-b']thiophene ( 83 ). 3,3'-Dibromo-6,6'-dimercapto-2,2'-bisthienothiophene ( 82 ) (8.6 g, 0.012 mol) was dissolved in THF (100 mL). This solution was cooled to -78 ° C under argon. Butyllithium (9.6 mL, 0.024 mol) was added dropwise to this solution, and the resulting mixture was stirred at -78 ° C for 30 minutes, and bis(phenylsulfonyl) sulfide (3.8 g, 0.012 mol) was added. ). This solution was stirred overnight at room temperature and then THF was evaporated. The residue was dissolved in hexane (300 mL). EtOAc was evaporated. Then the organic layer was dried on MgSO _4. After evaporating the solvent, the crude product was purified by column chromatography (hot hexane) to give a solid compound. This yellow compound was recrystallized from hexane to give 3.2 g (45.3%). Melting point: 107.7 ° C to 108.5 ° C. ¹ H NMR: solvent CD ₂ Cl ₂ . ¹ H NMR: 7.024 (s, 2H), 2.76 (t, 4H), 1.79-1.28 (m, 32H), 0.88 (t, 6H). ¹³ C NMR: 140.58, 138.96, 135.94, 129.80, 122.86, 105.64, 31.92, 29.77, 29.57, 29.33 (overlap), 28.69, 22.69, 14.11.

Referring to Figure 15A, 83 can also be prepared by cyclizing 87 with butyl lithium and copper chloride.

3,3'-Dibromo-5,5'-dimercapto-2,2'-bis-dithieno[3,2-b:2',3'-d]thiophene ( 85 ). Butyllithium (2.5 M in hexane, 4.4 mL, 0.011 mol) was added dropwise at 0 °C to a cone of diisopropylamine (1.13 g, 0.011 mol) in anhydrous THF (30 mL) bottle. The resulting mixture was kept at 0 ° C for 15 minutes. 3-Bromo-5-mercapto-dithieno[3,2-b:2',3'-d]thiophene ( 84 ) (4.61 g, 0.011 mol) was dissolved in THF (40 mL) Add by drop. This mixture was stirred at 0 ° C for 1 hour, and then copper (II) chloride (1.77 g, 0.013 mol) was added. This dark brown solution was stirred at room temperature for a further 12 hours. After evaporating all the solvent, the residue was boiled with toluene (2×200 mL) and the solid was filtered. After all the toluene was evaporated, the residue was boiled with toluene (200 mL) and cooled to room temperature. The crystallized solid was collected after cooling. This gave 2.0 g (43.8%). Melting point: 140.2 ° C to 141.1 ° C. ¹ H NMR: solvent CD ₂ Cl ₂ . ¹ H NMR: 7.11 (s, 2H), 2.78 (t, 4H), 1.75-1.28 (m, 32H), 0.86 (t, 6H).

3,7-diamidino-bis-dithieno{[3,2-b;4,5-d][2',3'-b;4',5'-d]}thiophene ( 86 ) . Dissolve 3,3'-dibromo-5,5'-dimercapto-bis-dithienothiophene ( 85 ) (3 g, 3.62 mmol) in dry tetrahydrofuran (80 mL) and cool to -78 ° C . Butyllithium (7.23 mmol, 2.9 mL) was added dropwise to this mixture under argon. The resulting mixture was stirred at -78 &lt;0&gt;C for 1 h then bis(phenylsulfonyl) sulfide (1.15 g, 3.62 mmol). The resulting mixture was stirred and slowly warmed to room temperature overnight. After evaporation of the THF, the residue was evaporated with water (200 mL) and filtered. The solid was then washed with methanol (2 x 50 mL) and refluxed with toluene (200 mL). The hot toluene solution was filtered to remove undissolved solids. After evaporating the toluene, the solid was redissolved in toluene (70 mL) and cooled to room temperature to give the title compound (1.68 g, 66. Melting point: 140.2-141.1 °C. ¹ H NMR: solvent CD ₂ Cl ₂ . ¹ H NMR: 7.11 (s, 2H), 2.78 (t, 4H), 1.79-1.28 (m, 32H), 0.88 (t, 6H).

Referring to Figure 15B, 86 can also be prepared by cyclizing 88 with butyl lithium and copper chloride.

Example 8: Synthesis of a tetraalkyl substituted thienothiophene dimer.

The synthesis of tricyclic and tetracyclic tetraalkyl-substituted thienothiophene dimers is shown in Figures 16 and 17, respectively.

Tricyclic dimer

2-Bromo-3-indolyldithieno[3,2-b:2',3'-d]thiophene ( 92 ). 3-Mercaptodithieno[3,2-b:2',3'-d]thiophene ( 91 ) (9.03 g, 0.027 mol) was dissolved in DMF (100 mL). N-bromosuccinimide (NBS) (4.78 g, 0.027 mol) in DMF (50 mL) was added dropwise to this solution under argon in the dark. The resulting mixture was stirred at 0 ° C for 3 hours. GC/MS showed a single peak at 415. Pour this solution into water (500 mL). The organic solution was extracted with hexane (3×100 mL). The combined organic solution was washed with concentrated brine (2 x 50 mL) and water (50 mL). After dried over MgSO _4, the hexane was evaporated. The crude product was purified by column chromatography eluting with hexane to afford the title compound (10.1 g, 90.2%). ¹ H NMR: solvent, CD ₂ Cl ₂ . ¹ H NMR: 7.39 (d, 1 H), 7.29 (d, 1 H), 2.74 (t, 2H), 1.74-1.33 (m, 16H), 0.89 (t, 3H). ¹³ C NMR: 140.89, 140.63, 136.00, 131.55, 129.22, 126.58, 121.04, 108.89, 32.31, 29.94, 29.73 (overlapping), 29.35, 28.49, 23.09, 14.27.

3-mercapto-6-indol-1-ynyldithieno[3,2-b:2',3'-d]thiophene ( 93 ). 2-Bromo-3-indolyldithieno[3,2-b:2',3'-d]thiophene ( 92 ) (4.16 g, 0.01 mol) and 1-decyne (3.6 g, 0.026 mol) Tetrakis(triphenylphosphine)palladium (0.58 g, 0.5 mmol) and copper (I) iodide (0.19 g, 1.0 mmol) were combined in triethylamine (80 mL). This mixture was bubbled with nitrogen for 5 minutes and then heated to 130 ° C under argon for 16 hours. Triethylamine was evaporated and hexane (150 mL) was added. This mixture was filtered to remove solid salts. The organic layer was 1 M hydrochloric acid (50 mL) and brine (50 mL) washed, and then dried over MgSO _4. The solvent was removed in vacuo and the residue was purified eluting elut elut ¹ H NMR: solvent CD ₂ Cl ₂ . ¹ H NMR: 7.36 (d, 1 H), 7.30 (d, 1H), 2.82 (t, 2H), 2.49 (t, 2H), 1.63-1.27 (m, 28H), 0.88 (m, 6H).

2,3-Dimercaptodithieno[3,2-b:2',3'-d]thiophene ( 94 ). 3-Mercapto-6-indol-1-ynyldithieno[3,2-b:2',3'-d]thiophene ( 93 ) (36.0 g, 0.076 mol) was dissolved in ethyl acetate (36.0 g, 0.076 mol) 60 mL). 5% Pt/C (9.0 g) was added to this solution. The mixture was stirred under an atmosphere of H ₂ (90 psi) 24 hours. The solution was then filtered. After the ethyl acetate was removed, the residue was purified by chromatography on silica gel eluting with hexane to afford the title compound (29.0 g, 79.9%). ¹ H NMR: solvent, CD ₂ Cl ₂ . ¹ H NMR: 7.29 (d, 1H), 7.27 (d, 1H), 2.80 (t, 2H), 2.67 (t, 2H), 1.68-1.27 (m, 32H), 0.88 (m, 6H). ¹³ C NMR: 142.88, 140.75, 139.82, 131.69, 131.37, 126.69, 125.04, 120.94, 32.16, 29.85 (m, overlap), 22.93, 14.11.

5,6,5'6'-tetradecyl-2,2'-bisdithieno[3,2-b:2',3'-d]thiophene ( 95 ). Butyllithium (4.5 mL, 0.011 mol) was added dropwise to the 2,3-dimercaptodithieno[3,2-b:2',3'-d]thiophene under argon at room temperature ( 94 ) (5.16 g, 0.011 mol) and N,N,N',N',-tetramethylethylenediamine (TMEDA) (1.25 g, 0.011 mol) in hexane. The resulting mixture was refluxed for 1 hour, and then copper (II) chloride powder was added to the reaction. This mixture was stirred overnight and the hexane was removed in vacuo. The residue was boiled with toluene (80 mL) and the solid residue was removed by filtration. The organic layer was concentrated with brine (2 × 30 mL) and water (30 mL) washed, and dried over MgSO _4. After the toluene was removed, the yellow solid was boiled with acetone (400 mL) and cooled to room temperature to afford crystals of compound (1.26 g, 24.5%). ¹ H NMR: solvent CD ₂ Cl ₂ . ¹ H NMR: 7.43 (s, 2H), 2.89 (t, 4H), 2.73 (t, 4H), 1.76-1.34 (m, 64H), 0.93 (m, 12H). ¹³ C NMR: solvent C ₆ D ₁₂ . ¹³ C NMR: 143.28, 141.09, 140.94, 138.12, 131.66, 131.41, 127.91, 117.18, 32.74, 32.63, 30.44, 30.39, 30.32, 30.29, 30.13, 29.86, 28.58, 23.41, 14.25.

Referring to Figure 16, 96 can also be prepared by cyclizing 95 with butyl lithium and bis(phenylsulfonyl) sulfide.

Tetracyclic dimer

2-Mercapto-3-bromo-5-mercaptodithieno[3,2-b:2',3'-d]thiophene ( 102 ). Butyl lithium (2.5 M in hexane, 10.9 mL, 0.0273 mol) was added dropwise to a cone of diisopropylamine (2.76 g, 0.027 mol) in anhydrous THF (100 mL) at 0 °C. . The resulting mixture was kept at 0 ° C for 15 minutes. 3-Bromo-5-mercapto-dithieno[3,2-b:2',3'-d]thiophene ( 101 ) (11.33 g, 0.0273 mol) was dissolved in THF (60 mL) Add the reaction dropwise. This mixture was kept at 0 ° C for 1 hour, and then 1-formylpiperidine was added. The resulting mixture was stirred overnight and the THF was removed. The residue was washed with 10% hydrochloric acid (30 mL) and water (3×100 mL). The solid target compound was purified by crystallization from ethanol (100 mL). This gave 8.80 g (72.8%). Melting point: 65.5 ° C to 67.2 ° C.

Ethyl 2-carboxylate-5-mercaptodithieno[2,3-d:2',3'-d']thieno[3,2-b:4,5-b']dithiophene 103 ). Dissolving 2-mercapto-3-bromo-5-mercaptodithieno[3,2-b:2',3'-d]thiophene ( 102 ) (8.80 g, 0.02 mol) in DMF (100 (mL) and mixed with potassium carbonate (9.66 g, 0.07 mol). A catalytic amount of 18-crown-6 ether was used as a catalyst. Ethyl thioglycolate (2.52 g, 0.021 mol) was added dropwise to this solution at 60 ° C to 70 ° C. The mixture was stirred at this temperature overnight. After reviewing the GC/MS, the mixture was poured into water (500 mL). The solid formed in the aqueous solution is removed by filtration. The solid was then washed with water (2 x 200 mL) and methanol (200 mL). GC/MS showed a single peak at 465. After drying in vacuo, the title compound was used without further purification (8.0 g, 86%). Melting point: 59.4 ° C to 62.0 ° C.

2-carboxylic acid-5-mercaptodithieno[2,3-d:2',3'-d']thieno[3,2-b:4,5-b']dithiophene ( 104 ) . Ethyl 2-carboxylate-3-bromo-5-mercaptodithieno[2,3-d:2',3'-d']thieno[3,2-b:4,5-b ']Dithiophene ( 103 ) (9.3 g, 0.02 mol) was dissolved in THF (100 mL). Methanol (20 mL) was added to this solution. LiOH (10% solution, 7 mL) was also added to this mixture. A catalytic amount of tetrabutylammonium iodide was used as a catalyst. This mixture was refluxed overnight. After removing 2/3 of the solvent, the residue was poured into cone. HCl (100 mL). The solid was collected by filtration and washed with water until neutralization. After drying, 6.06 g of the title compound was obtained (yield 69.3%). Melting point: 225 ° C to 227 ° C.

5-decyldithieno[2,3-d:2',3'-d']thieno[3,2-b:4,5-b']dithiophene ( 105 ). 2-carboxylic acid-5-mercaptodithieno[2,3-d:2',3'-d']thieno[3,2-b:4,5-b']dithiophene ( 104 (6.06 g, 0.014 mol) was dissolved in quinoline (80 mL). Copper powder (0.62 g, 9.7 mmol) was also added to this mixture. The mixture was heated to 240 ° C to 260 ° C until no air bubbles were observed (about 1 hour). The mixture was cooled to room temperature and poured into a 30% aqueous HCl solution (300 mL). The organic solution was extracted with hexane (150 mL) and washed several times with 10% HCl until the quinoline was removed from the organic layer. Then the organic layer was dried on MgSO _4. After removing the solvent, the residue was recrystallized from ethanol to give 4.44 g of the title compound (yield 81.3%). Melting point: 88.3 ° C to 89.6 ° C. ¹ H NMR: solvent CD ₂ Cl ₂ . ¹ H NMR: 7.38 (d, 1H), 7.32 (d, 1H), 6.99 (m, 1H), 2.73 (t, 2H), 1.77 (m, 2H), 1.35 - 1.27 (m, 14H), 0.87 (t) , 3H). ¹³ C NMR: 141.29, 140.59, 132.72, 133.51, 132.32, 132.27, 131.51, 126.29, 121.15, 121.02, 32.32, 30.00, 29.96, 29.78 (overlap), 29.73, 29.11, 23.09, 14.28.

2-Bromo-3-indolyldithieno[2,3-d:2',3'-d']thieno[3,2-b:4,5-b']dithiophene ( 106 ). NBS (2.01 g, 0.0113 mol) in DMF (30 mL) was added dropwise at 0 °C to 5-decyldithiophene [2,3-d in anhydrous DMF (50 mL). 2',3'-d'] thieno[3,2-b:4,5-b']dithiophene ( 105 ). The resulting mixture was stirred for 2 hours and poured into water (500 mL). The solid was filtered and washed several times with water. The crude compound was recrystallized using ethanol (200 mL) to give 5.06 g (94.9%). Melting point. ¹ H NMR: solvent CD ₂ Cl ₂ . ¹ H NMR: 7.43 (d, 1 H), 7.34 (d, 1H), 2.77 (t, 2H), 1.74 (m, 2H), 1.36.27 (m, 16H), 0.87 (t, 3H). ¹³ C NMR: 140.87, 139.54, 135.98, 133.31, 132.11, 131.70, 130.26, 126.77, 121.23, 109.03, 32.32, 29.99, 29.92, 29.75.29.66, 29.36, 28.50, 23.09, 14.28.

2-癸-1-ynyl-3-mercaptodithieno[2,3-d:2',3'-d']thieno[3,2-b:4,5-b'] Thiophene ( 107 ). 2-Bromo-3-indolyldithieno[2,3-d:2',3'-d']thieno[3,2-b:4,5-b']dithiophene (2.16 g) , 4.6 mmol) ( 106 ) with 1-decyne (1.27 g, 9.2 mmol), tetrakis(triphenylphosphine)palladium (0.27 g, 0.23 mmol) and copper (I) iodide (0.087 g, 0.46 mmol) Mix in triethylamine (50 mL). This mixture was bubbled with nitrogen for 5 minutes and then heated to 130 ° C under argon for 16 hours. Triethylamine was evaporated and hexane (150 mL) was added. This mixture was filtered to remove solid salts. The organic layer was washed with 1 M hydrochloric acid (50 mL) and brine (50 mL) and then dried over _MgSO the solvent was removed in vacuo and the residue was purified by chromatography, with hexane was eluted on a silica gel, to produce the target compound ^{(2.3 g, 90.2%) 1} HNMR:.. the solvent CD ₂ Cl ₂ ¹ H NMR: 7.41 (d, 1H), 7.33 (d, 1H), 2.84 (t, 2H), 2.23 (t, 2H), 1.73-1.27 (m, 28H), 0.89 (m, 6H) .

2,3-Dimercaptodithieno[2,3-d:2',3'-d']thieno [3,2-b:4,5-b']dithiophene ( 108 ). 2-癸-1-ynyl-3-mercaptodithieno[2,3-d:2',3'-d']thieno[3,2-b:4,5-b'] Dithiophene ( 107 ) (2.2 g, 4.15 mmol) was dissolved in ethyl acetate (30 mL). 5% Pt/C (0.5 g) was added to this solution. The mixture was stirred under an atmosphere of H ₂ (90 psi) 24 hours. The solution was then filtered. After the ethyl acetate was removed, the residue was purified by chromatography on silica gel eluting with hexane to give the title compound (2.00, 90.5%). Melting point: 50.9 ° C to 52.5 ° C. ¹ H NMR: solvent, CD ₂ Cl ₂ . ¹ H NMR: 7.41 (d, 1 H), 7.33 (d, 1 H), 2.83 (t, 2H), 2.50 (t, 2H), 1.73-1.26 (m, 32H), 0.87 (m, 6H). ¹³ C NMR: 140.85, 140.40, 139.93, 133.38, 133.14, 132.22, 129.69, 121.17, 120.09, 98.92, 32.29, 32.25, 29.99, 29.94, 29.72, 29.63, 29.52, 29.33, 29.18, 29.06, 28.94, 23.05, 14.23.

Referring to Figure 17, 109 can also be prepared by coupling 108 with butyl lithium and copper chloride. Cyclization of 109 to produce 110 can be accomplished by reacting 109 with butyllithium and bis(phenylsulfonyl) sulfide.

Example 9: Synthesis of a polymer comprising a cyclopentene molecular moiety

Poly-3,6-dihexyl-thieno[3,2-b]thiophene ( PDC6FT2 ) and poly-3,6- dimercapto -thieno[3,2-b]thiophene ( PDC10FT2 ) . The monomer 3,6-dihexyl-thieno[3,2-b]thiophene (3.08 g, 0.01 mol) was dissolved in chlorobenzene. A suspension of FeCl ₃ in chlorobenzene was added to the monomer solution over half an hour. The final concentrations for monomer and FeCl ₃ were 0.05 and 0.2 M, respectively. The mixture was stirred at room temperature for 6 hours to 24 hours. For larger ring sizes, the mixture can be heated to 80 ° C to 90 ° C for several hours. The polymer solution was poured into a 5% aqueous methanol solution and a precipitate formed. The polymer was collected by filtration and redissolved in toluene. The toluene solution was then boiled with concentrated aqueous ammonia (3 x 60 mL) followed by boiling twice with ethylenediaminetetraacetic acid (EDTA) (0.05 M in water) (2 x 50 mL). The obtained toluene was slowly added dropwise to methanol (500 mL) to precipitate a polymer. After filtration, the polymer was dried overnight in a vacuum oven (70 ° C to 80 ° C). The yields of PDC6FT2 and PDC10FT2 were 35% and 90%, respectively.

The above procedure was also used to produce polymer PDC10FT4 (80% yield) and PDC10 FTS3 (43% yield).

Example 10: Synthesis of bithiophene and cyclo-thiophene copolymer

2,6-Dibromo-3,5-dimercaptodithieno[3,2-b:2'3'-d]thiophene (1.0 g, 1.57 mmol), 2,5'-distannane Trimethyl-bis-thiophene (0.772 g, 1.57 mmol) and tetrakis(triphenylphosphine)palladium(0) (0.095 g, 0.082 mmol) were dissolved in chlorobenzene (30 mL) under argon. The resulting mixture was heated to 150 ° C under argon for 14 hours and then re-precipitated in methanol (400 mL). The collected solid polymer was washed with acetone (100 mL) and extracted with acetone in a Soxhlet extractor. followed by The solid polymer was dissolved in chlorobenzene (100 mL) and filtered through a glass filter. After most of the chlorobenzene was evaporated, the polymer shown below was again precipitated from methanol (300 mL). The red polymer powder was dried in vacuo to give 0.9 g (yield: 90.1%).

2,7-Dibromo-3,6-diamidinopentathiophene (0.89 g, 1.19 mmol), 2,5'-disienyltrimethyl-bisthiophene (0.59 g, 1.57 mmol) and Tetrakis(triphenylphosphine)palladium(0) (0.072 g, 0.062 mmol) was reacted in the manner described above. The polymer was extracted by hexane in a Soxhlet extractor. The final polymer shown below was dried in vacuo to give 0.8 g (yield: 89%).

2,8-Dibromo-3,7-dimercaptothieno[3,2-b]thieno[2',3':4,5]thieno[2,3-d]thiophene (1.0 g, 1.45 mmol), 1,4-bis-trimethylstannylbenzene (0.59 g, 1.45 mmol) and tetrakis(triphenylphosphine)palladium(0) (0.084 g, 0.073 mmol) were reacted in the manner described above. The polymer shown below was dried in vacuo to give 0.82 g (yield: 93.2%).

It will be apparent to those skilled in the art that various modifications and variations can be made in accordance with the invention without departing from the spirit and scope of the invention. And finished. Therefore, it is intended that the present invention cover the modifications and variations of the embodiments of the invention, and the modifications and variations of the specific embodiments are intended to be within the scope of the appended claims.

Example 11: Synthesis of a molecular moiety of a cyclohexyl-dione-pyrrolopyrrole and a polymer

The incorporation of a cyclohexaphene moiety into a polymer further comprising a diketopyrrolopyrrole ("DPP") moiety provides a number of advantages: 1) the absence of beta-hydrogen on the cyclopentene molecular moiety, which will result in DPP - the conjugated copolymer structure is more stable; 2) the potential to place a large alkyl-based R-group on the cyclopentene molecular moiety, providing improved solubility of the copolymer; 3) by larger conjugation The combination of cyclohexene thiophene units improves the electronic and optical properties of the DPP system.

The synthesis of the cyclopentadienyl-dionepyrrolopyrrole molecular moiety is as follows: 2,6-dibromo-3,7-heptadecylthieno[3,2-b]thieno[2',3 ',:4,5] Thieno[2,3-d]thiophene was synthesized as described herein. The dibromo-cyclo thiophene can then be continuously reacted with butyl lithium and trimethyltin chloride to form 2,6-bis(trimethylstannyl)-3,7- as shown in Figure 20. Di-heptadecylthieno[3,2-b]thieno[2',3',:4,5]thieno[2,3-d]thiophene ("P2TDC17FT4").

The formation of the molecular moiety of the dipyrrolopyrrole can be accomplished via the reaction scheme shown in Tieke et al. (Beilstein, J. Org. Chem. 830 (2010)), the entire contents of which is incorporated herein by reference, and In Figure 21, wherein the thiophene-2-carbonitrile is reacted with diisopropyl succinate to form 3,6-bis(thiophen-2-yl)pyrrolo[3,4-c] Pyrrole-1,4(2H,5H)-dione, which is then reacted with bromohexadecane and potassium carbonate to produce 2,5-di-heptadecyl-3,6-di(thiophen-2-yl) Pyrrolo[3,4-c]pyrrole-1,4(2H,5H)-dione. This reaction is then brominated via N-bromosuccinimide in dichloromethane and N,N-dimethylformamide to form 3,6-bis(5-bromothiophene). 2-yl)-2,5-di-heptadecylpyrrolo[3,4-c]pyrrole-1,4(2H,5H)-dione ("DC17DPP").

The cyclopentene and diketopyrrolopyrrole molecular moieties can be combined via any standard coupling reaction. As shown in Figure 22, N,N-dimethylformamide forms 3,6-bis(5-bromothien-2-yl)-2,5-di-heptadecylpyrrolo[3,4 -c]pyrrol-1,4(2H,5H)-dione is in the presence of the catalyst bis(triphenylphosphine)palladium(II) dichloride with 2,6-bis(trimethylstannane -3,7-di-heptadecylthieno[3,2-b]thieno[2',3',:4,5]thieno[2,3-d]thiophene is bonded to form Poly[(3,7-di-heptadecylthieno[3,2-b]thieno[2',3':4,5]thieno[2,3-d]thiophene-2,6- Dibasic) [2,5-di-heptadecyl-3,6-bis(thiophen-2-yl)pyrrolo[3,4-c]pyrrole-1,4(2H,5H)-dione] -5,5'-diyl ("PTDC17DPPTDC17FT4"). The reaction in Fig. 22 uses a palladium (II) catalyst because palladium (II) catalyst exhibits excellent reliability, but a palladium (O = 0) based catalyst can also be used (for example, tetrakis(triphenyl) Phosphine) palladium (0)).

A cyclohexaphene-based polymer (eg, P2TDC17FT4) has a higher mobility (hole) for charge transfer. This theoretical (and practical) limitation may be due to a change in the polymer structure, a partial substitution of the functionalized DPP molecule with mobility to replace the dithiophene molecule moiety. Start. The polymeric nature of PTDC17DPPTDC17FT4 is determined using standard test methods. The TGA measurements for the materials show that the material is thermally stable up to 400 ° C (Figure 23). TGA shows the binding of the DPP molecular moiety to the FT molecular moiety, surprisingly providing a copolymer with higher stability than DPP alone.

The color of the new PTDC17DPPTDC17FT4 polymer is very dark green, almost black, showing a wide range of absorption in the visible region of the solar spectrum. The chloroform solution and the UV-visible spectrum of the solid state of the film rotated from chloroform show broad absorption from about 550 nm to about 950 nm, and absorption from less than about 300 nm to 500 nm (Fig. 24). This covers a very wide range of visible light regions and gives the polymer a dark green, almost black appearance. One advantage of this material is its use in photovoltaic devices where such broad solar absorption is desired. Furthermore, in the same molecule, the current absorption extends beyond the IR is also highly desirable and is a unique property when combined with absorption down to 300 nm. This makes the polymer more efficient as a light absorber in organic photovoltaic devices because light capture efficiency is a major contributor to the light efficiency of photovoltaic systems. The intense optical interaction also makes this material a candidate for other optical and/or optoelectronic applications.

Example 12: Aryl-linked bicyclic thiophene structure

Poly[(3,7-di-heptadecylthieno[3,2-b]thieno[2',3':4,5]thieno[2,3-d]thiophene-2,6- Dibasic ) ( 2,1,3 -benzothiadiazole-4,7-diyl)] ( "P2BTDC17FT4" ) (Fig. 25): 2,6-dibromo-3,7-di-ten Heptacyclothieno[3,2-b]thieno[2',3',:4,5]thieno[2,3-d]thiophene (1.00 g, 0.94 mmol) and 4,7-dibromo Benzo[c]-1,2,5-thiadiazole (0.28 g, 0.94 mmol) was transferred to a three-necked conical flask containing a stir bar. Nitrogen was bubbled through this Erlenmeyer flask for a few minutes. After the conical flask is sealed, the conical flask is placed in the glove box. 0.055 g of Pd(PPh ₃ ) ₄ and 30 mL of anhydrous chlorobenzene were added to the Erlenmeyer flask. The Erlenmeyer flask was heated at approximately 130 ° C for 16 hours under nitrogen and then poured into a solution of methanol (200 mL) and concentrated hydrochloric acid (5 mL). The mixture was stirred overnight at room temperature. The precipitate was filtered and extracted with acetone in a Soxhlet apparatus overnight and then extracted with hexane overnight. The collected polymer was dried in vacuo to give 0.78 g of a blue polymer which was identified as poly[(3,7-di-heptadecylthiophene[3,2-b]thiophene[2',3 ':4,5]thieno[2,3-d]thiophene-2,6-diyl) (2,1,3-benzothiadiazole-4,7-diyl)]. (λ _{max is} in CHCl ₃ solution = 362 nm and 511 nm, λ _{max is} in the film = 511 nm and 578 nm. GPC (1,2,4-trichlorobenzene) Mn = 8200, Mw = 9,400; and PDI = 1.44) .

The accompanying drawings are included to provide a further understanding of this description and are incorporated in and constitute a part of this specification. The illustrations are not necessarily to scale, and the dimensions of the various elements may be modified for clarity. The illustrations illustrate one or more specific embodiments, and together with the description of the invention,

Figure 1 is a reaction scheme showing the method used to make the "" R-substituted cyclo-thiophene molecular moiety.

Figure 2 is a reaction scheme showing the method of producing the molecular moiety of α-(R-fluorenyl)-β-carboxymethylthiothiophene.

Figure 3 is a reaction scheme showing the method of making the alpha ' -hydrogen-β " -R-substituted cyclo-thiophene molecular moiety.

Figure 4 is a reaction scheme in which simultaneous cyclization is effected on both sides of the molecular portion of the thiophene.

Figure 5 is a reaction scheme showing another method for producing the molecular portion of α,α ' -bis(R-fluorenyl)-β,β ' -bis(carboxymethylthio)thiophene.

Figure 6 is a reaction scheme showing the method of producing pentacyclic cyclothiophene.

Figure 7 is a reaction scheme showing the preparation of a polycyclic ?-R-substituted-? ' -bromothiophene molecular moiety.

Figure 8 is a reaction scheme showing the method of producing a ?-R-substituted-? ' -bromothiophene compound.

Figure 9 is a reaction scheme showing the method of making a monosubstituted cyclothiophene.

Figure 10 is a reaction scheme showing the synthesis of 3,6-dihexylthieno[3,2-b]thiophene and 3,6-dimercaptothieno[3,2-b]thiophene according to Example 1.

Figure 11 is a reaction scheme showing the synthesis of 3-hexylthieno[3,2-b]thiophene according to Example 2.

Figure 12 is a reaction scheme showing 3,6-dimercaptothieno[3,2-b]thiophene and 3,6-dimercaptothieno[3,2-b]thiophene-4 according to Example 3. Synthesis of 4-dioxide.

Figure 13 is a reaction scheme showing 3,7-dimercaptothieno[3,2-b]thieno[2 ' ,3 ' :4,5]thieno[2,3-d according to Example 4. Synthesis of thiophene.

Figure 14 is a reaction scheme showing the failed synthesis of β-hexyl-substituted thieno[2,3-d]thiophene according to the conventional method contained in Example 5.

15A and 15B are reaction schemes for the synthesis of 2-2 and 3-3 dimers according to Example 7 and the five- and seven-ring systems.

Figure 16 is a reaction scheme for the synthesis of a heptacyclotetraalkyl substituted thienothiophene according to Example 8.

Figure 17 is a reaction scheme for the synthesis of a heterocyclic tetraalkyl substituted thienothiophene according to Example 8.

Figure 18 is a reaction scheme for the manufacture of a cyclohexene thiophene copolymer.

Figures 19A and 19B show the structure of different paracyclic thiophene copolymers made by the methods described herein.

Figure 20 shows the reaction scheme for the formation of bis-tin-substituted FT4 from dibromo-FT4 by sequential reaction with butyllithium and trimethyltin chloride.

Figure 21 illustrates the reaction scheme to produce bis-bromothienyl-DC17DPP (diketopyrrolopyrrole = "DPP").

Figure 22 illustrates the reaction scheme for coupling bis-tin-substituted FT4 (FT4 = four-membered cyclothiophene) to a bis-bromothienyl-DC17DPP via a palladium catalyzed Stille type coupling reaction.

Figure 23 shows that the polymerized PTDC17DPPTDC17FT4 material is thermally stable to temperatures in excess of 400 °C. This is a symbol of the stability of the polymer.

Figure 24 shows the ultraviolet-visible spectrum of a chloroform solution and a solid film of PTDC17DPPTDC17FT4 polymer. Both materials show broad absorption from about 550 nm to about 950 nm and less intense absorption from about 300 nm to 500 nm. These absorptions provide a dark, almost green-black appearance of the polymer, which is effective in photovoltaic systems.

Figure 25 illustrates the reaction scheme for forming a conjugated polymer comprising FT4 coupled by 4,7-benzo[c]-1,2,5-thiazole.

Claims (20)

A compound comprising the formula 3" or 4": Wherein m is an integer greater than 0; n is 1 or more; X and Y are independently a covalent bond or an aryl group; and R ₁ and R _{2 are} independently substituted or unsubstituted alkyl, substituted or Unsubstituted alkenyl, substituted or unsubstituted alkynyl, aryl, cycloalkyl, aralkyl, amine, ester, aldehyde, hydroxy, alkoxy, thiol, sulfanyl, halide , fluorenyl halide, acrylic acid or vinyl ether; R ₃ and R _{4 are} independently substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, aromatic a base, a cycloalkyl group, an aralkyl group, an amine group, an ester, an aldehyde, a hydroxyl group, an alkoxy group, a thiol group, a thioalkyl group, a halide, a decyl halide, an acrylic acid or a vinyl ether; and A and B are independently S or O. The compound of claim 1, wherein the compound comprises a polymer, wherein the polymer has a molecular weight of from about 400 Da to about 1800 Da. The compound of claim 1, wherein at least one of R ₁ and R ₂ comprises a substituted or unsubstituted alkyl group. The compound of claim 1, wherein at least one of R ₃ and R ₄ comprises a substituted or unsubstituted alkyl group. The compound of claim 4, wherein at least one of R ₃ and R ₄ comprises a substituted or unsubstituted alkyl group, the alkyl group comprising at least 6 carbon atoms. The compound of claim 1, wherein the compound is incorporated into a cyclo-thiophene polymer or oligomer having a conjugate of m>1. A compound, including Formula 100 or 101: Wherein a, m and n are independently an integer of 1 or greater; each X independently comprises an aryl group; and R ₁ and R _{2 are} independently substituted or unsubstituted alkyl, substituted or unsubstituted Substituted alkenyl, substituted or unsubstituted alkynyl, aryl, substituted or unsubstituted cycloalkyl, aralkyl, amine, ester, aldehyde, hydroxy, alkoxy, thiol, sulphur Alkyl, halide, sulfhydryl halide, acrylic acid or vinyl ether. The compound of claim 7, wherein X is: Wherein R ₃ and R _{4 are} independently substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, aryl, cycloalkyl, aralkyl, Amine, ester, aldehyde, hydroxy, alkoxy, thiol, thioalkyl, halide, sulfhydryl halide, acrylic acid or vinyl ether; and Z is hydrogen, substituted or unsubstituted alkyl, substituted Or unsubstituted alkenyl, substituted or unsubstituted alkynyl, aryl, substituted or unsubstituted cycloalkyl, aralkyl, amine, ester, aldehyde, hydroxy, alkoxy, sulphur An alcohol, a sulfanyl group, a halide, a decyl halide, an acrylic acid or a vinyl ether or a covalent bond; and Y is a bond linking X to the cyclohexylphenyl group or one or more aryl groups. The compound of claim 7, wherein the compound comprises a polymer, wherein the polymer has a molecular weight of from about 400 Da to about 1800 Da. The compound of claim 1, wherein at least one of R ₃ and R ₄ comprises a substituted or unsubstituted alkyl group. The compound of claim 7, wherein the compound is incorporated into a cyclo-thiophene polymer or oligomer having a conjugate of m>1. A device comprising the compound of claim 1 or 7, wherein the device comprises a transistor (FET), a thin film transistor (TFT), an organic light emitting diode (OLED), and an optoelectronic (EO) device. , a conductor material, a pair of photon hybrid materials, an organic semiconductor, an RFID tag, an electro-laser device or a photovoltaic and sensor device. A method of producing a compound according to claim 1, comprising the steps of: (i) providing one of the structures 1 or 2 and a cyclothiophene molecular moiety; Wherein R ₁ and R _{2 are} independently substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, aryl, cycloalkyl, aralkyl, Amine, ester, aldehyde, hydroxyl, alkoxy, thiol, thioalkyl, halide, sulfhydryl halide, acrylic acid or vinyl ether; and X and Y are independently Sn(Alk) ₃ , wherein Alk is once a substituted or unsubstituted alkyl group; (ii) providing a dipyrrolopyrrole molecular moiety of structure 3: Wherein X and Y are independently an aryl group comprising a halide; (iii) coupling the moiety of the cyclopentaphene molecule of structure 1 or 2 to the moiety of the dipyrrolopyrrole of structure 3 via a catalytic reaction. The method of claim 13, wherein the catalytic reaction is a metal catalyzed reaction. The method of claim 14, wherein the metal catalyzed reaction is a Stille type coupling. The method of claim 14, further comprising polymerizing the compound of Formula 3" or 4". A method of producing a compound according to claim 7 comprising the steps of: (i) providing one of the structures 1 or 2 and a cyclothiophene molecular moiety; Wherein R ₁ and R _{2 are} independently substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, aryl, substituted or unsubstituted ring Alkyl, aralkyl, amine, ester, aldehyde, hydroxyl, alkoxy, thiol, thioalkyl, halide, sulfhydryl halide, acrylic or vinyl ether; X and Y are independently Sn(Alk) ₃ wherein Alk is a substituted or unsubstituted alkyl group or a substituted or unsubstituted cycloalkyl group; (ii) an aryl molecule moiety which provides a double substitution of structure 3 or 4: Sn(Alk) ₃ - Q-Sn(Alk) ₃ 3 Ha-Q-Ha 4 wherein Q is a conjugate group, Ha is a halogen, and Alk is a substituted or unsubstituted alkyl group or a substituted or unsubstituted cycloalkyl group; (iii) coupling the cyclized thiophene molecule moiety of structure 1 or 2 to the aryl molecular moiety of structure 3 or 4 via a catalytic reaction; wherein when X and Y are halogen, compound 3 is used, and When X and Y are Sn(Alk) ₃ , compound 4 is used. The method of claim 17, wherein Q is: Wherein R ₃ and R _{4 are} independently substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, aryl, cycloalkyl, aralkyl, Amine, ester, aldehyde, hydroxyl, alkoxy, thiol, thioalkyl, halide, sulfhydryl halide, acrylic acid or vinyl ether; and Z' is hydrogen, substituted or unsubstituted alkyl, Substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, aryl, substituted or unsubstituted cycloalkyl, aralkyl, amine, ester, aldehyde, hydroxy, alkoxy, a thiol, a sulfanyl group, a halide, a decyl halide, an acrylic acid or a vinyl ether or a covalent bond; and Y is a bond linking Q to the cyclohexylphenyl group or one or more aryl groups. The method of claim 17, wherein the catalytic reaction is a metal catalyzed reaction. The method of claim 17, further comprising polymerizing a compound of formula 100 or 101.