WO2009123695A1 - Fused thiophenes and methods for making and using same - Google Patents
Fused thiophenes and methods for making and using same Download PDFInfo
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- WO2009123695A1 WO2009123695A1 PCT/US2009/001965 US2009001965W WO2009123695A1 WO 2009123695 A1 WO2009123695 A1 WO 2009123695A1 US 2009001965 W US2009001965 W US 2009001965W WO 2009123695 A1 WO2009123695 A1 WO 2009123695A1
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- 0 CCC1C(C*2)C2=CC1 Chemical compound CCC1C(C*2)C2=CC1 0.000 description 13
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- C07D495/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms in which the condensed system contains two hetero rings
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- C07D495/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms
- C07D495/22—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms in which the condensed system contains four or more hetero rings
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- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic System
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- C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
- C08G61/122—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides
- C08G61/123—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds
- C08G61/126—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds with a five-membered ring containing one sulfur atom in the ring
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- C09K19/00—Liquid crystal materials
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- C09K19/06—Non-steroidal liquid crystal compounds
- C09K19/34—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring
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- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
- C08G2261/32—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain
- C08G2261/324—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain condensed
- C08G2261/3243—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain condensed containing one or more sulfur atoms as the only heteroatom, e.g. benzothiophene
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- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
- C08G2261/36—Oligomers, i.e. comprising up to 10 repeat units
- C08G2261/364—Oligomers, i.e. comprising up to 10 repeat units containing hetero atoms
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Definitions
- the present invention relates, generally, to heterocyclic organic compounds and, more particularly, to fused thiophene compounds and to methods for making and using same.
- Highly conjugated organic materials are currently the focus of great research activity, chiefly due to their interesting electronic and optoelectronic properties. They are being investigated for use in a variety of applications, including field effect transistors (FETs), thin-film transistors (TFTs), organic light-emitting diodes (OLEDs), electro-optic (EO) applications, as conductive materials, as two photon mixing materials, as organic semiconductors, and as non-linear optical (NLO) materials.
- FETs field effect transistors
- TFTs thin-film transistors
- OLEDs organic light-emitting diodes
- EO electro-optic
- Highly conjugated organic materials may find utility in devices such as radio frequency identification (RFID) tags, electroluminescent devices in flat panel displays, and in photovoltaic and sensor devices.
- RFID radio frequency identification
- Oligomers and polymers of fused thiophenes such as oligo- or poly(thieno[3,2-6]thiophene (2) and oligo- or poly(dithieno[3,2-6:2'-3'- ⁇ i]thiophene) (1) - 2 - Attorney Docket No. SP08-086PCT have also been suggested for use in electronic and optoelectronic devices and have been shown to have acceptable conductivities and non-linear optical properties. [0005]
- We have described some fused thiophene-based materials in U.S. Patent Application No. US2007/0161776 of He and in PCT Patent Application Publication No. WO 2006/031893 of He.
- a need for new fused thiophenes and methods for making fused thiophenes continues to exist, and the present invention is directed, in part, to addressing this need.
- the present invention relates to a compound having one of the following formulae 11 or 12:
- X is an aromatic nucleophilic substitution leaving group
- R 1 is hydrogen, an alkyl group, or an aryl group
- Q 1 is a carboxyl protecting group or an aldehyde protecting group.
- the present invention also relates to a compound having one of the following formulae 14, 15, 16, or 17:
- R 1 and R 2 are the same or different and are selected from hydrogen, alkyl, and aryl;
- Q 3 and Q 4 are independently selected from hydrogen, a carboxylic acid, a carboxylic acid derivative, an alkyl group, an aryl group, an aldehyde group, an aldehyde derivative, a ketone group, a hydroxyl group, an unsubstituted thiol group, a substituted thiol group, an alkoxy group, an acrylate group, an amino group, a vinyl group, a vinyl ether group, or a halide; and Q 2 has one of the following formulae 18, 19, 20, 21 A, or 21B:
- R 3 and R 4 are the same or different and are selected from alkyl and aryl.
- the present invention also relates to a compound having the following formula 23:
- Z 1 has one of the following formulae wherein Z 1 has one of the following formulae 24A, 24B, 24C, 24D, 25, 26, 27, 28, 29, or 30: - 4 - Attorney Docket No. SP08-086PCT
- the present invention also relates to a compound having one of the following formulae 37, 38, 39, or 40:
- R 12 , R 13 , and R 14 are independently selected from alkyl and aryl.
- the present invention also relates to a compound having one of the following formulae 41, 42, 43, 44, 45,or 46:
- R 15 is selected from hydrogen, alkyl, and aryl; wherein Q 12 is selected from hydrogen, a carboxylic acid, a carboxylic acid derivative, an alkyl group, an aryl group, an aldehyde group, an aldehyde derivative, a ketone group, a hydroxyl group, an unsubstituted thiol group, a substituted thiol group, an alkoxy group, an acrylate group, an amino group, a vinyl group, a vinyl ether group, or a halide; and wherein Q 13 has the formula:
- R 12 , R 13 , and R 14 are independently selected from alkyl and aryl.
- Figures IA and IB are synthetic schemes that can be used to prepare certain compounds of the present invention.
- Figures 2A-2C are synthetic schemes that can be used to prepare certain compounds of the present invention.
- Figures 3 A and 3 B are synthetic schemes that can be used to prepare certain compounds of the present invention.
- Figure 4 is a synthetic scheme that can be used to prepare certain compounds of the present invention.
- Figure 5 is a synthetic scheme that can be used to prepare certain compounds of the present invention.
- Figures 6A-6D are synthetic schemes that can be used to prepare certain compounds of the present invention.
- Figure 7 is a synthetic scheme showing a prior art method for preparing fused thiophenes.
- Figures 8 and 9 are a synthetic scheme comparing prior art methods and compounds for preparing fused thiophenes to certain methods and compounds of the present invention.
- Figures 10 and 11 are synthetic schemes that can be used to prepare certain compounds of the present invention.
- Ranges may be expressed herein as from “about” one particular value, and/or to "about” another particular value. When such a range is expressed, another aspect includes from the one particular value and/or to the other particular value. Similarly, when values are expressed as approximations, by use of the antecedent "about”, it will be understood that the particular value forms another aspect. It will be further understood that the endpoints of each of the ranges are significant both in relation to the other endpoint, and independently of the other endpoint.
- a weight percent of a component is based on the total weight of the formulation or composition in which the component is included.
- alkyl group is a saturated hydrocarbon group of 1 to 40 carbon atoms.
- alkyl is meant to include linear alkyls, branched alkyls, and cycloalkyls, each of which can be substituted or unsubstituted.
- Alkyl is also meant to include lower linear alkyls (e.g., C1-C6 linear alkyls), such as methyl, ethyl, n- propyl, n-butyl, n-pentyl, and n-hexyl; lower branched alkyls (e.g., C3-C8 branched alkyls), such as isopropyl, t-butyl, 1-methylpropyl, 2-methylpropyl, 1-methylbutyl, 2- methylbutyl, 3-methylbutyl, 1 ,2-dimethylpropyl, 1,1-dimethylpropyl, 2,2-dimethylpropyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1,1-dimethylbutyl, 1,2- dimethylbutyl, 1,3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3, 3,
- alkyl is meant to include unsubstituted alkyls, such as those set forth above, in which no atoms other than carbon and hydrogen are present.
- Alkyl is also meant to include substituted alkyls.
- Suitable substituents include aryl groups (which may themselves be substituted), heterocyclic rings (saturated or unsaturated and optionally substituted), alkoxy groups (which is meant to include aryloxy groups (e.g., phenoxy groups)), amine groups (e.g., disubstituted with aryl or alkyl groups), carboxylic acid derivatives (e.g., carboxylic acid esters, amides, etc.), halogen atoms (e.g., Cl, Br, and I), and the like.
- aryl groups which may themselves be substituted
- heterocyclic rings saturated or unsaturated and optionally substituted
- alkoxy groups which is meant to include aryloxy groups (e.g., phenoxy groups)
- amine groups e.g., disubstituted with aryl or alkyl groups
- carboxylic acid derivatives e.g., carboxylic acid esters, amides, etc.
- halogen atoms
- alkyl groups bearing one or more alkenyl or alkynyl substituents e.g., a methyl group itself substituted with a prop-1-en-l-yl group to produce a but-2-en-l-yl substituent
- alkyl e.g., a methyl group itself substituted with a prop-1-en-l-yl group to produce a but-2-en-l-yl substituent
- suitable substituents include hydroxy groups and protected hydroxy groups (e.g., an acyloxy group, such at an acetoxy group; a silyl ether group, such as a trimethylsilyl (TMS) ether group and a tert- butyldimethylsilyl (TBS) ether group; and the like).
- TMS trimethylsilyl
- TBS tert- butyldimethylsilyl
- the alkyl group can be substituted or unsubstituted.
- unsubstituted alkyl group is defined herein as an alkyl group composed of just carbon and hydrogen.
- substituted alkyl group is defined herein as an alkyl group with one or more hydrogen atoms substituted with a group including, but not limited to, an aryl group, cycloalkyl group, aralkyl group, an alkenyl group, an alkynyl group, an amino group (e.g., an unsubstituted amino group, a monosubstituted amino group, or a disubstituted amino group), a carboxylic acid, an amide, an ester, an aldehyde, a hydroxyl group, an alkoxy group, a thiol group (which may be unsubstituted or substituted with, for example, and alkyl or aryl group), a halide, an acyl halide, an acrylate, or a vinyl ether.
- alkyl group as used herein also includes cycloalkyl groups.
- cycloalkyl group as used herein is a non-aromatic carbon-based ring composed of at least three carbon atoms. Examples of cycloalkyl groups include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, etc.
- the term cycloalkyl group also includes a heterocycloalkyl group, where at least one of the carbon atoms of the ring is replaced with a heteroatom such as, but not limited to, nitrogen, oxygen, sulfur, or phosphorus.
- alkyl group as used herein also includes aralkyl groups.
- aralkyl as used herein is - 10 - Attorney Docket No. SP08-086PCT
- an alkyl group having an aryl group (as defined herein) attached to the alkyl group is an alkyl group having an aryl group (as defined herein) attached to the alkyl group.
- An example of an aralkyl group is a benzyl group.
- alkoxy is meant to include groups having the formula -O-R, where R is an alkyl or aryl group. They include methoxy, ethoxy, propoxy, phenoxy, A- methylphenoxy, and the like.
- aryl is meant to include aromatic rings, for example, aromatic rings having from 4 to 12 members, such as phenyl rings. These aromatic rings can optionally contain one or more heteroatoms (e.g., one or more of N, O, S, and P), and, thus, "aryl", as used herein, is meant to include heteroaryl moieties, such as thienyl rings, pyridyl rings, and furanyl rings. The aromatic rings can be optionally substituted. "Aryl” is also meant to include aromatic rings to which are fused one or more other aryl rings or non-aryl rings.
- naphthyl groups, indole groups, thienothienyl groups, dithienothienyl, and 5,6,7,8-tetrahydro-2-naphthyl groups are aryl groups for the purposes of the present application. As indicated above, the aryl rings can be optionally substituted.
- Suitable substituents include alkyl groups (which can optionally be substituted), other aryl groups (which may themselves be substituted), heterocyclic rings (saturated or unsaturated), alkoxy groups (which is meant to include aryloxy groups (e.g., phenoxy groups)), hydroxy groups, aldehyde groups, nitro groups, amine groups (e.g., unsubstituted, or mono- or di- substituted with aryl or alkyl groups), carboxylic acid groups, carboxylic acid derivatives (e.g., carboxylic acid esters, amides, etc.), halogen atoms (e.g., Cl, Br, and I), and the like.
- alkyl groups which can optionally be substituted
- other aryl groups which may themselves be substituted
- heterocyclic rings saturated or unsaturated
- alkoxy groups which is meant to include aryloxy groups (e.g., phenoxy groups)), hydroxy groups, aldehyde groups, nitro
- ring refers to a homocyclic or heterocyclic ring which can be saturated or unsaturated, aromatic or non-aromatic.
- the ring can be unsubstituted, or it can be substituted with one or more substituents.
- the substituents can be saturated or unsaturated, aromatic or nonaromatic, and examples of suitable substituents include those recited above in the discussion relating to substituents on alkyl and aryl groups.
- two or more ring substituents can combine to form another ring, so that "ring", as used herein, is meant to include fused ring systems.
- the ring may optionally include unsaturated (aromatic or nonaromatic) or saturated substituents.
- alkenyl group is defined as a branched or unbranched hydrocarbon group of 2 to 40 carbon atoms containing at least one carbon-carbon double bond.
- alkynyl group is defined as a branched or unbranched hydrocarbon group of 2 to 40 carbon atoms containing at least one carbon-carbon triple bond.
- each of the combinations A-E, A-F, B-D, B-E, B-F, C-D, C-E, and C-F are specifically contemplated and should be considered disclosed from disclosure of A, B, and C; D, E, and F; and the example combination A-D.
- any subset or combination of these is also specifically contemplated and disclosed.
- the sub-group of A-E, B-F, and C-E is specifically contemplated and should be considered disclosed from disclosure of A, B, and C; D, E, and F; and the example combination A-D.
- One aspect of the present invention relates to a compound having one of the following formulae 11 or 12: - 12 - Attorney Docket No. SP08-086PCT wherein X is an aromatic nucleophilic substitution leaving group; R 1 is hydrogen, an alkyl group, or an aryl group; and Q 1 is a carboxyl protecting group or an aldehyde protecting group.
- Examples of carboxyl protecting groups include esters, thioesters, and oxazolines.
- Examples of aldehyde protecting groups include acetals, such as cyclic acetals.
- choice of a particular carboxyl protecting group or aldehyde protecting group will depend on the use to which compounds of formula 11 or formula 12 are to be put. For example, in those cases where compounds of formula 11 or formula 12 are to be used as starting materials in further syntheses (such as the syntheses described below), the particular carboxyl protecting group or aldehyde protecting groups would be chosen based on its stability to subsequent reaction conditions, the availability of deprotection chemistries that are compatible with other substituents that might be present, etc.
- linear alkyl esters e.g., linear C1-C8 alkyl esters, such as methyl esters, for example, where Q 1 is -COOCH 3
- tertiary alkyl esters e.g., tertiary C4-C8 alkyl esters, such as t-butyl esters, for example, where Q 1 is -COOC(CH 3 ) 3
- aralkyl esters e.g., (C6-C10)aryl-substituted-(Cl-C4)alkyl esters, such as benzyl esters, for example, where Q 1 is -COOCH 2 (CeH 5 )
- tertiary alkyl thioesters e.g., tertiary C4-C8 alkyl thioesters, such as t-butyl thioesters, for example, where Q 1 is
- R 1 and R 11 are the same or different and are selected from hydrogen, alkyl (e.g., a substituted or unsubstituted C1-C8 alkyl), and aryl (e.g., a substituted or unsubstituted phenyl) or R 10 and R 11 , together with the carbon atom to which they are bound, form a ring (e.g., a 4- to 8-membered (such as a 5-membered, 6-membered, etc.) homocyclic or - 13 - Attorney Docket No. SP08-086PCT
- R 10 and R 11 can be the same or different lower alkyl, such as in the case where R 10 and R 11 are the same or different and are selected from a C1-C6 alkyl.
- R 10 and R 11 are the same lower alkyl, for example as in the case where each of R 10 and R 11 is a methyl group, an ethyl group, a n-propyl group, and i-propyl group, etc.
- X is an aromatic nucleophilic substitution leaving group.
- aromatic nucleophilic substitution leaving group is meant to refer to those leaving groups appropriate to aromatic nucleophilic substitution, such as those disclosed in March, Advanced Organic Chemistry (4th edition), Wiley Interscience, 1992, page 652, which is hereby incorporated by reference.
- suitable leaving groups include F, Cl, Br, I, and sulfonic esters (e.g. tosylate, mesylate, besylate, and triflate).
- R 1 can be a hydrogen, an alkyl group, or an aryl group.
- R 1 can be a variety of substituted or unsubstituted alkyl groups.
- R 1 can be an unsubstituted alkyl group, such as a straight-chain alkyl group (e.g. methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl or hexadecyl), a branched alkyl group (e.g.
- R 1 is an alkyl group at least four carbons in size. In certain embodiments, R 1 is a substituted alkyl group at least four carbons in size. In certain embodiments, R 1 is a substituted alkyl group at least four carbons in size in which substitution of the alkyl group is separated from the fused thiophene ring system by at least two carbons.
- R 1 is a substituted alkyl group (e.g., an alkyl group substituted with an aryl group, a cycloalkyl group, an aralkyl group, an alkenyl group, an alkynyl group, an amino group, an ester, an aldehyde, a hydroxyl group, an alkoxy group, a thiol group, a thioalkyl group, a halide, an acyl halide, an acrylate, or a vinyl ether).
- substituted alkyl groups include, but are not limited to, 6-hydroxyhexyl and 3- phenylbutyl. The selection of R 1 can depend on the end use of the compound.
- the aforementioned compounds having formula 11 or 12 can be prepared by any suitable method.
- thiophene 50 e.g., dibromothiophene
- an acid chloride e.g., acid chloride 51
- a Friedel-Crafts compatible Lewis acid such as a stoichiometric amount OfAlCl 3
- Ketone 52 can be converted to thienothiophene ester 54, for example, by reaction with 2-mercaptoacetate 53 (e.g., in which R 50 is an alkyl or aryl group, such as an ethyl group or another unsubstituted C1-C4 alkyl group) in the presence of a base, such as potassium carbonate.
- 2-mercaptoacetate 53 e.g., in which R 50 is an alkyl or aryl group, such as an ethyl group or another unsubstituted C1-C4 alkyl group
- a base such as potassium carbonate
- Thienothiophene ester 54 can be converted to thienothiophene free acid 56, for example by hydrolyzing thienothiophene ester 54 in the presence of lithium hydroxide, followed by acidification (e.g., with hydrochloric acid).
- Thienothiophene free acid 56 can be converted to oxazolinyl thienothiophene 58 by converting the free acid to the corresponding acid chloride (using, for example, thionyl chloride, oxalyl chloride, etc.), followed by reaction of the acid chloride with l-amino-2-hydroxyalkane 57 (e.g., in which R 10 and R 11 are the same or different and are selected from hydrogen, alkyl, and aryl or in R 10 and R 11 , together with the carbon atom to which they are bound, form a ring, for example as described above), followed by treatment with a dehydrating agent, such as thionyl chloride, phosphorus pentoxide, oxalyl chloride, and the like.
- a dehydrating agent such as thionyl chloride, phosphorus pentoxide, oxalyl chloride, and the like.
- thienothiophene 60 e.g., dibromothienothiophene
- an acid chloride e.g., acid chloride 61
- OfAlCl 3 or other Friedel-Crafts compatible Lewis acid e.g., a stoichiometric amount of AlCl 3
- Ketone 62 can be converted to dithienothiophene ester 64, for example, by reaction with 2-mercaptoacetate 63 (e.g., in which R 50 is an alkyl or aryl group, such as an ethyl group or another unsubstituted C1-C4 alkyl group) in the presence of potassium carbonate or another base.
- Dithienothiophene ester 64 can be converted to dithienothiophene free acid 66, for example by hydrolyzing dithienothiophene ester 64 in the presence of lithium hydroxide, followed by acidification (e.g., with hydrochloric acid).
- Dithienothiophene free acid 66 can be converted to oxazolinyl dithienothiophene 68 by converting the free acid to the - 15 - Attorney Docket No. SP08-086PCT
- the X groups in the beta positions of thiophene 50 and thienothiophene 60 can be the same or they can be different.
- both X moieties can be the same halogen, as in the case where both X's are Br.
- the two X moieties can be different, as in the case where both one X is Br and the other X is F or as in the case where one X is a halogen (e.g., Br) and the other X is, for example, a triflate group.
- the present invention in another aspect thereof, relates to a compound having one of the following formulae 14, 15, 16, or 17:
- R 1 and R 2 are the same or different and are selected from hydrogen, alkyl, and aryl;
- Q 3 and Q 4 are independently selected from hydrogen, a carboxylic acid, a carboxylic acid derivative, an alkyl group, an aryl group, an aldehyde group, an aldehyde derivative, a ketone group, a hydroxyl group, an unsubstituted thiol group, a substituted thiol group, an alkoxy group, an acrylate group, an amino group, a vinyl group, a vinyl ether group, or a halide; and Q 2 has one of the following formulae 18, 19, 20, 21A, or 21B:
- R and R 4 are the same or different and are selected from alkyl and aryl.
- Q 3 and Q 4 are the same. In certain embodiments, Q 3 and Q 4 are different. In certain embodiments, Q 3 , Q 4 , or both Q 3 and Q 4 can be an aldehyde group or an aldehyde derivative. Examples of aldehyde derivatives include - 21 - Attorney Docket No. SP08-086PCT
- Q 3 , Q 4 , or both Q 3 and Q 4 can be a carboxylic acid or a carboxylic acid derivative.
- carboxylic acid derivatives include carboxylic acid esters (e.g., substituted alkyl esters, unsubstituted alkyl esters, substituted C1-C6 alkyl esters, unsubstituted Cl- C6 alkyl esters, substituted aryl esters, unsubstituted aryl esters, etc.); carboxylic acid amides (e.g., unsubstituted amides, monosubstituted amides, disubstituted amides, etc.); acyl halides (e.g., acyl chlorides, etc.); carboxyl protecting groups; and the like.
- carboxylic acid esters e.g., substituted alkyl esters, unsubstituted alkyl esters, substituted C1-C6 alkyl esters, unsubstituted Cl- C6 alkyl esters, substituted aryl esters, unsubstituted aryl esters, etc.
- Q 3 , Q 4 , or both Q 3 and Q 4 can be a carboxyl protecting group.
- carboxyl protecting groups include esters, thioesters, and oxazolines.
- linear alkyl esters e.g., linear C1-C8 alkyl esters, such as methyl esters, for example, where Q 3 , Q 4 , or both Q 3 and Q 4 are -COOCH 3
- tertiary alkyl esters e.g., tertiary C4-C8 alkyl esters, such as t-butyl esters, for example, where Q 3 , Q 4 , or both Q 3 and Q 4 are -COOC(CH 3 ) 3
- aralkyl esters e.g., (C6-C10)aryl-substituted- (Cl-C4)alkyl esters, such as benzyl esters, for example, where Q 3 , Q 4
- Q 3 , Q 4 , or both Q 3 and Q 4 can be an oxazoline moiety, such as a l,3-oxazolin-2-yl moiety, for example, as in the case where Q 3 , Q 4 , or both Q 3 and Q 4 have the formula:
- R 10 and R 11 are the same or different and are selected from hydrogen, alkyl (e.g., a substituted or unsubstituted C1-C8 alkyl), and aryl (e.g., a substituted or unsubstituted phenyl) or R 10 and R 11 , together with the carbon atom to which they are bound, form a ring (e.g., a 4- to 8-membered (such as a 5-membered, 6-membered, etc.) homocyclic or heterocyclic ring).
- alkyl e.g., a substituted or unsubstituted C1-C8 alkyl
- aryl e.g., a substituted or unsubstituted phenyl
- R 10 and R 11 can be the same or different lower alkyl, such as in the case where R 10 and R 11 are the same or different and are selected from a C1-C6 alkyl.
- R 10 and R 11 are the same lower alkyl, for example as in the case where each of R 10 and R 11 is a methyl group, an ethyl group, a n-propyl group, and i-propyl group, etc. - 22 - Attorney Docket No. SP08-086PCT
- R 1 and R 2 can be the same or different, each being independently selected from a hydrogen, an alkyl group, or an aryl group.
- R 1 and/or R 2 can be a variety of substituted or unsubstituted alkyl groups.
- R 1 and/or R 2 can be an unsubstituted alkyl group, such as a straight-chain alkyl group (e.g.
- R 1 and/or R 2 is an alkyl group at least four carbons in size.
- R 1 and/or R 2 is a substituted alkyl group at least four carbons in size. In certain embodiments, R 1 and/or R 2 is a substituted alkyl group at least four carbons in size in which substitution of the alkyl group is separated from the fused thiophene ring system by at least two carbons.
- R 1 and/or R 2 is an alkyl group substituted with an aryl group, cycloalkyl group, aralkyl group, an alkenyl group, an alkynyl group, an amino group, an ester, an aldehyde, a hydroxyl group, an alkoxy group, a thiol group, a thioalkyl group, a halide, an acyl halide, an acrylate, or a vinyl ether.
- substituted alkyl groups include, but are not limited to, 6-hydroxyhexyl and 3-phenylbutyl.
- both R 1 and R 2 are hydrogen atoms, hi certain embodiments, R 1 is a hydrogen atom, and R 2 is an alkyl group, such as one of the alkyl groups mentioned above. In certain embodiments, R 2 is a hydrogen atom, and R 1 is an alkyl group, such as one of the alkyl groups mentioned above, hi certain embodiments both R 1 and R 2 are the same alkyl group, hi certain embodiments R 1 represents one alkyl group, R 2 represents a different alkyl group. As with the selection of R 1 in the context of compounds having the formula 11 or 12, selection of R 1 and/or R 2 here can depend on the end use of the compound.
- R 3 and R 4 can be the same or different, and each is independently selected from an alkyl group or an aryl group.
- R 3 and/or R 3 can be a substituted alkyl group, an unsubstituted alkyl group, a substituted aryl group, or an unsubstituted aryl group.
- Suitable examples of R 3 and R 4 groups include those mentioned above with regard to R 1 and R 2 . - 23 - Attorney Docket No. SP08-086PCT
- compounds having formula 14 in which Q 2 has formula 18 can be prepared following the procedures described in Figure 2 A from compounds of the present invention having formula 12 and a bis(trialkyltin) sulfide, such as a bis(tri(C2- C6)alkyltin) sulfide, a bis(tri(C3-C4)alkyltin) sulfide, and/or a bis(tributyltin) sulfide.
- a bis(trialkyltin) sulfide such as a bis(tri(C2- C6)alkyltin) sulfide, a bis(tri(C3-C4)alkyltin) sulfide, and/or a bis(tributyltin) sulfide.
- oxazolinyl thienothiophenes 58a and 58b are reacted with bis(tributyltin) sulfide 70 to produce compound 72.
- Compounds having formula 15 in which Q 2 has formula 18 can be prepared following the procedures described in Figure 2B from compounds of the present invention having formula 11 and a bis(trialkyltin) sulfide, such as those mentioned above.
- oxazolinyl dithienothiophenes 68a and 68b (each of which can be separately prepared in accordance with the procedures described in Figure IB) can be reacted with bis(tributyltin) sulfide 70 to produce compound 74.
- oxazolinyl thienothiophene 58a (which can be prepared in accordance with the procedures described in Figure IA) is reacted with an alkyl lithium compound (e.g., butyl lithium), followed by reaction with sulfur and then with a trialkyl tin halide (e.g., tributyl tin chloride) to produce tin sulfide thienothiophene 76.
- Tin sulfide thienothiophene 76 can then be reacted with oxazolinyl dithienothiophene 68b (which can be prepared in accordance with the procedures described in Figure IB) to produce compound 78.
- - 24 Attorney Docket No. SP08-086PCT
- compounds having formula 14 in which Q 2 has formula 19, 20, 21A, or 21B can be prepared following the procedures described in Figure 3 A from compounds of the present invention having formula 12 and a di(trialkyltin sulfide) thiophene or a di(trialkyltin sulfide) thienothiophene, such as a di(tri(C2- C6)alkyltin sulfide) thiophene or a di(tri(C2-C6)alkyltin sulfide) thienothiophene, a di(tri(C3-C4)alkyltin sulfide) thiophene or a di(tri(C3-C4)alkyltin sulfide) thienothiophene, and/or a di(tributyltin sulfide) thiophene or a di(tributyltin sulfide)
- oxazolinyl thienothiophenes 58a and 58b are reacted with di(trialkyltin sulfide) thiophene or di(trialkyltin sulfide) thienothiophene 80 to produce compound 82.
- compounds having formula 15 in which Q 2 has formula 19, 20, 21A, or 21B can be prepared following the procedures described in Figure 3 B from compounds of the present invention having formula 11 and a di(trialkyltin sulfide) thiophene or a di(trialkyltin sulfide) thienothiophene, such as those mentioned above.
- oxazolinyl dithienothiophene 68a and 68b are reacted with di(trialkyltin sulfide) thiophene or di(trialkyltin sulfide) thienothiophene 84 to produce compound 86.
- compounds having formula 14 in which Q 2 has formula 22A, 22B, 22C, 22D, or 22E can be prepared from compounds of the present invention having formula 12 following procedures similar to that described in Figure 3 A; and compounds having formula 15 in which Q 2 has formula 22 A, 22B, 22C, 22D, or 22E can be prepared from compounds of the present invention having formula 11 following procedures similar to that described in Figure 3B.
- a compound of the present invention having formula 12 e.g., oxazolinyl dithienothiophene 58a and 58b (each of which can be separately prepared in accordance with the procedures described in Figure IA)
- a compound of the present invention having formula 11 e.g., oxazolinyl - 25 - Attorney Docket No. SP08-086PCT
- dithienothiophene 68a and 68b (each of which can be separately prepared in accordance with the procedures described in Figure IB)) can be treated with butyl lithium (or another alkyl lithium) to produce the corresponding beta anion, and the resulting beta anion can then be reacted with an appropriate reagent, such as a selenium dihalide (e.g., SeCl 2 ) to produce compounds having formula 14 or 15 in which Q 2 has formula 22 A; a tellurium dihalide (e.g., TeCl 2 ) to produce compounds having formula 14 or 15 in which Q 2 has formula 22B; an alkyl or aryl boron dihalide (e.g., R 3 BCl 2 , in which R 3 is an alkyl or aryl group) to produce compounds having formula 14 or 15 in which Q 2 has formula 22C; a dihalo alkyl phosphine or dihalo aryl phosphine (e.g., R 3 PBr 2
- the product is shown to have terminal thiophene rings bearing an oxazoline moiety in the alpha position (i.e., compounds having formula 14, 15, 16, or 17 in which Q 3 and Q 4 are an oxazoline groups).
- an oxazoline group can be readily converted to the carboxylic acid (for example, by treatment with HCl or another strong acid), and the carboxylic acid can be converted to esters, amides, and other carboxylic acid derivatives using conventional procedures.
- carboxylic acids and carboxylic acid derivatives can then be converted to hydrogen (e.g., compounds having formula 14, 15, 16, or 17 in which Q 3 and Q 4 are hydrogen atoms) or other functional groups, such as those described above.
- hydrogen e.g., compounds having formula 14, 15, 16, or 17 in which Q 3 and Q 4 are hydrogen atoms
- other functional groups such as those described above.
- the aforementioned compounds having formulae 14, 15, 16, or 17 can be used in a variety of synthetic and other procedures, examples of which will be apparent from the discussion that follows.
- the present invention in another aspect thereof, relates to a compound having the formula:
- Z 1 has one of the following formulae 24A, 24B, 24C, 24D, 25, 26, 27, 28, 29, or 30: - 26 - Attorney Docket No. SP08-086PCT
- examples of compounds of formula 23 in which Z 1 has formula 24A include those set forth below:
- R 1 and R 2 can be the same, or they can be different; and each is independently selected from a hydrogen, an alkyl group, or an aryl group.
- R 1 and/or R 2 can be a variety of substituted or unsubstituted alkyl groups.
- R 1 and/or R 2 can be an unsubstituted alkyl group, such as a straight-chain alkyl group (e.g.
- R 1 and/or R 2 is an alkyl group at least four carbons in size.
- R 1 and/or R 2 is a substituted alkyl group at least four carbons in size. In certain embodiments, R 1 and/or R 2 is a substituted alkyl group at least four carbons in size in which substitution of the alkyl group is separated from the fused thiophene ring system by at least two carbons.
- R 1 and/or R 2 is an alkyl group substituted with an aryl group, cycloalkyl group, aralkyl group, an alkenyl group, an alkynyl group, an amino group, an ester, an aldehyde, a hydroxyl group, an alkoxy group, a thiol group, a thioalkyl group, a halide, an acyl halide, an acrylate, or a vinyl ether.
- substituted alkyl groups include, but are not limited to, 6-hydroxyhexyl and 3-phenylbutyl.
- both R 1 and R 2 are hydrogen atoms, hi certain embodiments, R 1 is a hydrogen atom, and R 2 is an alkyl group, such as one of the alkyl groups mentioned above, hi certain embodiments, R 2 is a hydrogen atom, and R 1 is an alkyl group, such as one of the alkyl groups mentioned above, hi certain embodiments both R 1 and R 2 are the same alkyl group, hi certain embodiments R 1 represents one alkyl group, R 2 represents a different alkyl group.
- selection of R 1 in the context of compounds having the formula 11 or 12 selection of R 1 and/or R 2 here can depend on the end use of the compound.
- each T is S (i.e., a sulfur atom), hi certain embodiments, at least one T is SO 2 . hi certain embodiments, at least one of the three or four central-most Ps is SO 2 and the remaining T's are S, for example, as in the case where the compound has formula 24A, 26, 28, or 30, at least one (e.g., one, two, three, or four) of the four central -most Ts is SO 2 , and the remaining Ts are S; and as in the case where - 31 - Attorney Docket No. SP08-086PCT
- the compound has formula 24B, 25, 27, or 29, at least one (e.g., one, two, or three) of the three central-most T's is SO 2 , and the remaining T's are S.
- each T is independently S or SO 2 , where T is SO 2 in at least one of the central-most rings of the fused thiophene ring system.
- the central-most ring of a fused thiophene ring system having an odd number 2q+l of fused rings is the q+l ⁇ ring from an end of the ring system.
- the central-most rings of a fused thiophene ring system having an even number 2q of fused rings are the q ⁇ and q+l ⁇ rings from an end of the ring system.
- the central- most ring of a five-ring system is the third ring
- the central-most rings of a six-ring system are the third and fourth rings
- the central-most ring of a seven-ring system is the fourth ring.
- Z 1 has one of the formulae 24A or 24B.
- at least one of Q 5 and Q 6 is a thioester, an oxazoline, or an acetal.
- each of Q 5 and Q 6 is a thioester or an oxazoline, and Q 5 and Q 6 are the same.
- each of Q 5 and Q 6 is an oxazoline, and Q 5 and Q 6 are the same.
- each of Q 5 and Q 6 is an acetal, and Q 5 and Q 6 are the same.
- one of Q 5 and Q 6 is a thioester, an oxazoline, or an acetal; and the other of Q 5 and Q 6 is hydrogen, a carboxylic acid, a carboxylic acid derivative, an alkyl group, an aldehyde group, an aldehyde derivative, a ketone group, a hydroxyl group, an unsubstituted thiol group, a substituted thiol group, an alkoxy group, an acrylate group, an amino group, a vinyl group, a vinyl ether group, or a halide.
- At least one of Q 5 and Q 6 is an oxazoline moiety, such as a l,3-oxazolin-2-yl moiety, for example, as in the case where at least one of Q 5 and Q 6 has the formula:
- R 10 and R 11 are the same or different and are selected from hydrogen, alkyl (e.g., a substituted or unsubstituted C1-C8 alkyl), and aryl (e.g., a substituted or unsubstituted phenyl) or R 10 and R 11 , together with the carbon atom to which they are bound, form a ring (e.g., a 4- to 8-membered (such as a 5-membered, 6-membered, etc.) homocyclic or heterocyclic ring).
- R 10 and R 11 can be the same or different lower alkyl, - 32 - Attorney Docket No. SP08-086PCT
- R 10 and R 11 are the same or different and are selected from a C1-C6 alkyl.
- R 10 and R 11 are the same lower alkyl, for example as in the case where each of R 10 and R 11 is a methyl group, an ethyl group, a n-propyl group, and i-propyl group, etc.
- Z 1 has one of the formulae 24C, 24D, 25, 26, 27, 28, 29, or 30.
- Q 5 and Q 6 are the same or different and are selected from hydrogen, a carboxylic acid, a carboxylic acid derivative, an alkyl group, an aryl group, an aldehyde group, an aldehyde derivative, a ketone group, a hydroxyl group, an unsubstituted thiol group, a substituted thiol group, an alkoxy group, an acrylate group, an amino group, a vinyl group, a vinyl ether group, or a halide.
- Q 5 and Q 6 are the same, hi certain embodiments, Q 5 and Q 6 are different.
- at least one of Q 5 and Q 6 is a hydrogen, such as in the case where each of Q 5 and Q 6 is a hydrogen, hi certain embodiments, at least one of Q 5 and Q is an aldehyde group, such as in the case where each of Q 5 and Q 6 is an aldehyde group, hi certain embodiments, at least one of Q 5 and Q 6 is an aldehyde derivative, such as in the case where each of Q 5 and Q 6 is an aldehyde derivative.
- aldehyde derivatives include aldehyde protecting groups, such as acetals (e.g., cyclic acetals).
- at least one of Q 5 and Q 6 is a carboxylic acid, such as in the case where each of Q 5 and Q 6 is a carboxylic acid.
- at least one of Q 5 and Q 6 is a carboxylic acid derivative, such as in the case where each of Q 5 and Q 6 is a carboxylic acid derivative.
- carboxylic acid derivatives include carboxylic acid esters (e.g., substituted alkyl esters, unsubstituted alkyl esters, substituted C1-C6 alkyl esters, unsubstituted C1-C6 alkyl esters, substituted aryl esters, unsubstituted aryl esters, etc.); carboxylic acid amides (e.g., unsubstituted amides, monosubstituted amides, disubstituted amides, etc.); acyl halides (e.g., acyl chlorides, etc.); carboxyl protecting groups; and the like, hi certain embodiments, at least one of Q 5 and Q 6 is a carboxyl protecting group, such as in the case where each of Q 5 and Q 6 is a carboxyl protecting group.
- carboxylic acid esters e.g., substituted alkyl esters, unsubstituted alkyl esters, substituted C1-C
- carboxyl protecting groups include esters, thioesters, and oxazolines.
- linear alkyl esters e.g., linear C1-C8 alkyl esters, such as methyl esters, for example, where Q 5 , Q 6 , or both Q 5 and Q 6 are - COOCH 3
- tertiary alkyl esters e.g., tertiary C4-C8 alkyl esters, such as t-butyl esters, for example, where Q 5 , Q 6 , or both Q 5 and Q 6 are -COOC(CH 3 ) 3
- aralkyl esters e.g., (C6- - 33 - Attorney Docket No. SP08-086PCT
- C10)aryl-substituted-(Cl-C4)alkyl esters such as benzyl esters, for example, where Q 5 , Q 6 , or both Q 5 and Q 6 are -COOCH 2 (C 6 H 5 )); and tertiary alkyl thioesters (e.g., tertiary C4-C8 alkyl thioesters, such as t-butyl thioesters, for example, where Q 5 , Q 6 , or both Q 5 and Q 6 are -C(O)SC(CH 3 ) 3 ).
- tertiary alkyl thioesters e.g., tertiary C4-C8 alkyl thioesters, such as t-butyl thioesters, for example, where Q 5 , Q 6 , or both Q 5 and Q 6 are -C(O)SC(CH 3 ) 3 ).
- Q 5 , Q 6 , or both Q 5 and Q 6 can be an oxazoline moiety, such as a l,3-oxazolin-2-yl moiety, for example, as in the case Q 5 Q , or both Q 5 and Q 6 have the formula:
- R 10 and R 11 are the same or different and are selected from hydrogen, alkyl (e.g., a substituted or unsubstituted C1-C8 alkyl), and aryl (e.g., a substituted or unsubstituted phenyl) or R 10 and R 11 , together with the carbon atom to which they are bound, form a ring (e.g., a 4- to 8-membered (such as a 5-membered, 6-membered, etc.) homocyclic or heterocyclic ring).
- alkyl e.g., a substituted or unsubstituted C1-C8 alkyl
- aryl e.g., a substituted or unsubstituted phenyl
- R 10 and R 11 can be the same or different lower alkyl, such as in the case where R 10 and R 11 are the same or different and are selected from a C1-C6 alkyl.
- R 10 and R 11 are the same lower alkyl, for example as in the case where each of R 10 and R 11 is a methyl group, an ethyl group, a n-propyl group, and i-propyl group, etc.
- Q 5 and Q 6 can be the same or different and selected from hydrogen, a carboxylic acid, a carboxylic acid derivative, an alkyl group, an aryl group, an aldehyde group, an aldehyde derivative, a ketone group, a hydroxyl group, an unsubstituted thiol group, a substituted thiol group, an alkoxy group, an acrylate group, an amino group, a vinyl group, a vinyl ether group, or a halide.
- These groups can be chosen, for example, based on the use to which the compound is to be put.
- choice of Q 5 and Q 6 can be based, in whole or in part, on a group's ability to participate in subsequent reactions (e.g., polymerization reactions or cross-linking reactions), on a group's reactivity or inertness, on a group's ability to affect solubility of the compound in a particular solvent or class of solvents, and the like.
- Q 5 and Q 6 can be selected for their ability to function as electron donors and/or electron acceptors in donor- acceptor chromophores.
- Q 5 and Q 6 can be chosen such that one of Q 5 and Q 6 is an electron donating group and the other of Q 5 and Q 6 is an electron accepting - 34 - Attorney Docket No. SP08-086PCT
- electrostatic donating group refers to substituents which contribute electron density to a compound's pi-electron system when the compound's electron structure is polarized by the input of electromagnetic energy.
- a compound of the present invention can be a donor-acceptor chromophore
- chromophore as used herein, referring to an optical compound comprising an electron donating group and an electron accepting group at opposing termini of a conjugated pi electron system.
- Donor-acceptor chromophores, as well as suitable electron donating groups and electron accepting group, are described in U.S. Patent No. 6,584,266 to He et al., U.S.
- Z 1 has one of the formulae 24C, 24D, 25, 26, 27, 28, 29, or 30, and Q 5 and Q 6 are chosen such that at least one of Q 5 and Q 6 is an aryl group having the following formula 31:
- Z 2 has one of formulae 24A, 24B, 24C, 24D, 25, 26, 27, 28, 29, or 30 and wherein Q 7 is selected from hydrogen, a carboxylic acid, a carboxylic acid derivative, an alkyl group, an aryl group, an aldehyde group, an aldehyde derivative, a ketone group, a hydroxyl group, an unsubstituted thiol group, a substituted thiol group, an alkoxy group, an acrylate group, an amino group, a vinyl group, a vinyl ether group, and a halide.
- Q 7 is selected from hydrogen, a carboxylic acid, a carboxylic acid derivative, an alkyl group, an aryl group, an aldehyde group, an aldehyde derivative, a ketone group, a hydroxyl group, an unsubstituted thiol group, a substituted thiol group, an alkoxy group, an acrylate group, an amino
- R 21 , R 22 , R 23 , and R 24 can be the same, or they can be different; and each is independently selected from the moieties recited above for R 1 and R 2 (i.e., hydrogen, an alkyl group, or an aryl group), and each T is independently selected from S and SO 2 .
- R 1 and R 2 i.e., hydrogen, an alkyl group, or an aryl group
- each T is independently selected from S and SO 2 .
- Z 1 and Z 2 can be the same, or Z 1 and Z 2 can be different.
- Q 5 and Q 6 can be the same (e.g., in cases where Z 2 and Q 7 is the same for each of Q 5 and Q 6 ); or Q 5 and Q 6 can be different (e.g., as in the case where Q 5 's Z 2 is different than Q 6l s Z 2 and/or where Q 5 's Q 7 is different than Q 6 's Q 7 ).
- Q 6 is an aryl group having formula 31, and Q 5 and Q 7 are selected such that one of Q 5 and Q 7 is an electron donating group, and the other of Q 5 and Q 7 is an electron accepting group.
- Q 5 is an aryl group having formula 31, and Q 6 and Q 7 are selected such that one of Q 6 and Q 7 is an electron donating group and the other of Q 6 and Q 7 is an electron accepting group, hi certain embodiments, both Q 5 and Q 6 are aryl groups having formula 31, for example, as in the case where the compound has the following formula 33:
- Q7— Z 2— Z 1 Z 2 Q7 33j and the Q 7 's are selected such that one Q 7 is an electron donating group and the other Q 7 is an electron accepting group.
- Z 1 has one of the formulae 24C, 24D, 25, 26, 27, 28, 29, or 30, and Q 5 and Q 6 are chosen such that at least one of Q 5 and Q 6 is an aryl group having the following formula 34:
- each Z 3 is independently selected from formulae 24A, 24B, 24C, 24D, 25, 26, 27, 28, 29, and 30; each Z 4 is the same or different and is an aryl group; Q 7 is selected from hydrogen, a carboxylic acid, a carboxylic acid derivative, an alkyl group, an aryl group, an aldehyde group, an aldehyde derivative, a ketone group, a hydroxyl group, an unsubstituted thiol group, a substituted thiol group, an alkoxy group, an acrylate group, an amino group, a vinyl group, a vinyl ether group, and a halide; each p is the same or different and is zero or an integer greater than zero and each q is the same or different and is zero or an integer greater than zero, provided that at least one p or at least one q is not zero; and x is greater than or equal to one.
- aryl groups that can be used as Z 4 in the above formula 34 include aromatic rings that can undergo a Stille reaction.
- suitable Z 4 groups include benzene rings (e.g., a benzene ring bonded via the - 37 - Attorney Docket No. SP08-086PCT
- naphthalene rings e.g., a naphthalene ring bonded via the 2 and 6 positions
- heteroaryl rings such as 5-membered heteroaryl rings, for example, thiophene rings (e.g., a thiophene ring bonded via the thiophene ring's alpha positions) and furan rings (e.g., a furan ring bonded via the furan ring's alpha positions).
- suitable Z 4 groups there can be mentioned those of the following formulae:
- suitable values for p include 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, from 15 to 20, from 20 to 50, from 50 to 100, and the like;
- suitable values for q include 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, from 15 to 20, from 20 to 50, from 50 to 100, and the like;
- suitable values for x include 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, from 15 to 20, from 20 to 50, from 50 to 100, from 100 to 200, from 200 to 500, from 500 to 1000, and the like;
- the compound contains more than one unit having formula 35, and the p values and the q values for each unit can be the same (e.g., as in the case where the units are repeating units) or the p values and/or the q values for each unit can be different (e.g., as in the case where the units are randomly-selected or otherwise non-repeating units).
- the compound When x is one, the compound contains only one unit having formula 35, and the number of Z 3 units is p. When p is one, there is only one Z 3 unit. When p is greater than one, there is more than one Z unit, and these Z 3 units can be the same, or they can be different. Similarly, when x is one, the compound contains only one unit having formula 35, and the number of Z 4 units is q. When q is one, there is only one Z 4 unit. When q is - 38 - Attorney Docket No. SP08-086PCT
- Z 4 unit there is more than one Z 4 unit, and these Z 4 units can be the same, or they can be different.
- the compound When x is greater than one, the compound contains more than one unit having formula 35, the number of Z 3 units is x multiplied by p, and these Z 3 units can be the same, or they can be different. Similarly, when x is greater than one, the compound contains more than one unit having formula 35, the number of Z 4 units is x multiplied by q, and these Z 4 units can be the same, or they can be different.
- aryl groups having formula 34 are meant to include groups in which each q is zero, for example, as in the case where the aryl group has the following formula:
- each q is zero, and each p is one. In certain embodiments, each q is zero, each p is one, and each Z 3 is the same.
- aryl groups having formula 34 are meant to include groups in which each p is zero, for example, as in the case where the aryl group has the following formula:
- aryl groups having formula 34 are meant to include groups in which at least one p is an integer greater than zero and in which at least one q is an integer greater than zero, examples of which include:
- each q is the same and is an integer greater than zero
- each p is the same and is an integer greater than zero
- each Z 3 is the same
- each Z 4 is the same.
- each q is the same and is an integer greater than zero
- each p is one.
- each q is the same or different and is one, two, or three; and each p is the same or different and is one, two, or three. In certain embodiments, each q is the same and is one, two, or three; and each p is the same and is one, two, or three. In certain embodiments, each q is the same and is one, two, or three; each p is the same and is one, two, or three; each Z 3 is the same; and each Z 4 is the same.
- Examples of compounds having formula 23 in which Z 1 has one of the following formulae 24C, 24D, 25, 26, 27, 28, 29, or 30 and in which Q 5 and Q 6 are chosen such that at least one of Q 5 and Q 6 is an aryl group having formula 34 include those having the formulae set forth below: - 40 - Attorney Docket No. SP08-086PCT
- R 21 , R 22 , R 23 , and R 24 are the same or different and each is independently selected from the moieties recited above for R 1 and R 2 (i.e., hydrogen, an alkyl group, or an aryl group); in which each T is independently selected from S and SO 2 ; and in which x is an integer greater than zero.
- the aforementioned compounds have formula 23 in which Z 1 has one of the following formulae 24C, 24D, 25, 26, 27, 28, 29, or 30; in which one of Q 5 and Q 6 is an aryl group having formula 34; in which the other of Q 5 and Q 6 is an electron donating group or an electron accepting group; in which, when the other of Q 5 and Q 6 is an electron donating group, Q 7 is an electron accepting group; and in which, when the other of Q 5 and Q 6 is an electron accepting group, Q 7 is an electron donating group.
- Q 6 is an aryl group having formula 34; one of Q 5 and Q 7 is an electron donating group; and the other of Q 5 and Q 7 is an electron accepting group.
- Q 5 is an aryl group having formula 34; one of Q 6 - 41 - Attorney Docket No. SP08-086PCT
- Q 6 and Q 7 is an electron donating group; and the other of Q 6 and Q 7 is an electron accepting group.
- the aforementioned compounds have formula 23 in which Z 1 has one of the following formulae 24C, 24D, 25, 26, 27, 28, 29, or 30; in which one of Q 5 and Q 6 is an aryl group having formula 34; and in which the other of Q 5 and Q 6 is an aryl group having the formula:
- each Z 5 is independently selected from formulae 24A, 24B, 24C, 24D, 25, 26, 27, 28, 29, and 30; wherein each Z 6 is the same or different and is an aryl group; wherein one of Q 7 and Q 8 is an electron donating group or an electron accepting group; wherein, when Q 7 is an electron donating group, Q 8 is an electron accepting group; wherein, when Q 7 is an electron accepting group, Q 8 is an electron donating group; and wherein each r is the same or different and is zero or an integer greater than zero and each t is the same or different and is zero or an integer greater than zero, provided that at least one r or at least one t is not zero; and y is greater than or equal to one.
- Compounds of the present invention having formula 23 wherein Z 1 has one of the formulae 24A, 24B, 24C, 24D, 25, 26, 27, 28, 29, or 30 can be prepared by any suitable method.
- compounds of formula 23 in which Z 1 has formula 24B wherein m is 2 or in which Z 1 had formula 24C can be prepared from compounds of the present invention having formula 14 in which Q 2 has formula 18, 22A, 22B, 22C, 22D, or 22E.
- compound 72 e.g., prepared in accordance with the procedures described in Figure 2A when Q 2 is S or in accordance with the procedures described above when Q 2 is -Se-, -Te-, -B(R 3 )-, -P(R 3 )-, or -Si(R 3 )(R 4 )-
- an alkyl lithium e.g., butyl lithium
- a copper halide e.g., CuCl 2
- iron salt e.g., iron acetate
- Compounds of formula 23 in which Z 1 has formula 24A in which n is 3 can be prepared from compounds having formula 16 or 17 in which Q 2 has formula 18.
- compound 78 e.g., prepared in accordance with the procedures described in Figure 2C
- an alkyl lithium e.g., butyl lithium
- a copper halide - 42 - Attorney Docket No. SP08-086PCT
- compound 74 (e.g., prepared in accordance with the procedures described in Figure 2B when Q 2 is S or in accordance with the procedures described above when Q is -Se-, -Te-, -B(R 3 )-, -P(R 3 )-, or -Si(R 3 )(R 4 )-) can be treated with an alkyl lithium (e.g., butyl lithium) and a copper halide (e.g., CuCl 2 ) or iron salt (e.g., iron acetate) to produce a compound of formula 23 in which Z 1 has formula 24B in which n is 3.
- an alkyl lithium e.g., butyl lithium
- a copper halide e.g., CuCl 2
- iron salt e.g., iron acetate
- Compounds of formula 23 in which Z 1 has formula 24B in which m is 3 can alternatively be prepared from compounds having formula 14 in which Q 2 has formula 19 using an alkyl lithium (e.g., butyl lithium) and a copper halide (e.g., CuCl 2 ) or iron salt (e.g., iron acetate).
- alkyl lithium e.g., butyl lithium
- copper halide e.g., CuCl 2
- iron salt e.g., iron acetate
- the starting materials (compounds having formula 14, 15, 16, or 17) can have terminal thiophene rings bearing an oxazoline - 43 - Attorney Docket No. SP08-086PCT
- alkyl lithium e.g., butyl lithium
- copper halide e.g., CuCl 2
- the oxazoline moiety can be readily converted (e.g., subsequent to treatment with alkyl lithium and copper halide) to the carboxylic acid (for example, by treatment with aqueous HCl), and the carboxylic acid can be converted to esters, amides, and other carboxylic acid derivatives using conventional procedures.
- the aforementioned free carboxylic acids or carboxylic acid derivatives can then be converted to hydrogen, an alkyl group, an aldehyde group, an aldehyde derivative, a ketone group, a hydroxyl group, an unsubstituted thiol group, a substituted thiol group, an alkoxy group, an acrylate group, an amino group, a vinyl group, a vinyl ether group, a halide, etc. using conventional procedures.
- compounds of formula 23 having terminal thiophene rings bearing an oxazoline moiety in the alpha position can be converted to compounds of formula 23 having terminal thiophene rings bearing a carboxylic acid in the alpha position by treatment with aqueous HCl; and the carboxylic acid group can then be removed by conventional procedures, for example, by treatment with copper.
- FIG. 4 A typical reaction sequence is illustrated in Figure 4, in which a compound having thiophene rings bearing an oxazoline moiety in the alpha position (compound 90) is converted to a compound having thiophene rings bearing a carboxylic acid in the alpha position (compound 91) and then to a compound having thiophene rings having unsubstituted alpha positions (compound 92).
- compounds of formula 23 having terminal thiophene rings bearing hydrogen in the alpha position can be converted to compounds of formula 23 having terminal thiophene rings bearing a halogen in the alpha position by treatment with a halogenating agent, such as N-bromosuccinimide.
- a halogenating agent such as N-bromosuccinimide.
- Compounds of formula 23 having terminal thiophene rings bearing a halogen in the alpha position can be readily converted to compounds of formula 23 having terminal thiophene rings bearing an aryl group in the alpha position by reaction with an aryl trialkyltin, such as an aryl trialkyltin - 44 - Attorney Docket No. SP08-086PCT
- R 25 having the formula (R 25 ) 3 Sn-Ar, wherein Ar comprises an aryl group and R 25 is an alkyl group.
- the coupling reaction can be performed in the presence of a catalyst, for example, a palladium catalyst, such as a Pd(O) catalyst, examples of which include Pd(PPh 3 ) 4 .
- a catalyst for example, a palladium catalyst, such as a Pd(O) catalyst, examples of which include Pd(PPh 3 ) 4 .
- compounds of formula 23 having one terminal thiophene ring bearing hydrogen in the alpha position can be converted to compounds having formula 23 in which Q 6 has formula 31 (e.g., compounds having 32) using iron(i ⁇ ) compounds, such as FeCl 3 or Fe(acac) 3 .
- such compounds can be prepared from compounds of formula 23 having one terminal thiophene ring bearing a halogen (e.g., Br) in the alpha position using organomagnesium mediated chemistries.
- a halogen e.g., Br
- compounds of formula 23 having both terminal thiophene rings bearing hydrogen in the alpha positions can be converted to conjugated oligomers or polymers (e.g., having formula 23 in which Q 6 has formula 34 in which q is zero) using UOn(IH) compounds, such as FeCl 3 or Fe(acac) 3 .
- conjugated oligomers or polymers e.g., having formula 23 in which Q 6 has formula 34 in which q is zero
- conjugated oligomers or polymers e.g., having formula 23 in which Q 6 has formula 34 in which q is not zero.
- compounds of formula 23 having both terminal thiophene rings bearing a halogen in the alpha positions can be readily converted to compounds of formula 23 in which Q 6 has formula 34 wherein q is not zero by reaction with an aryl bis(trialkyltin), such as an aryl bis(trialkyltin) having the formula (R 25 ) 3 Sn-Z 4 -Sn(R 25 ) 3 , wherein Z 4 comprises an aryl group and R 25 is an alkyl group, for example, by performing the coupling reaction in the presence of a catalyst (e.g., a palladium catalyst, such as a Pd(O) catalyst, examples of which include Pd(PPh 3 ) 4 .
- a catalyst e.g., a palladium catalyst, such as a Pd(O) catalyst, examples of which include Pd(PPh 3
- Figure 5 illustrates one embodiment of this method.
- a compound of formula 23 having both terminal thiophene rings bearing halogen in the alpha positions i.e., compound 96
- compound 95 which can be prepared from a compound of formula 23 having both terminal thiophene rings bearing hydrogen in the alpha positions (i.e., compound 95), e.g., by treatment with N-bromosuccinimide
- distannyl aromatic compound 97 e.g., a 2,5'- - 45 - Attorney Docket No. SP08-086PCT
- distannyltrimethyl-bithiophene in the presence of Pd(PPh 3 )4 to produce compound 98.
- suitable Z 4 moieties for use in distannyl aromatic compound 97 and compound 98 include those set forth above in the discussion regarding formula 34. [0098] Using the methodologies described above, one skilled in the art can prepare oligomers, polymers, copolymers (e.g., block copolymers, condensation copolymers, etc.), and other compounds having formula 23 in which Q 6 has formula 34.
- such oligomers, polymers, copolymers, and other compounds having formula 23 in which Q 6 has formula 34 possess enhanced packing ability and thermal stability hi certain embodiments, they display liquid crystalline phases over certain temperature ranges, and the liquid crystalline properties can be tuned, for example, by choice of the groups R 1 and R 2 (e.g., by changing the length of R 1 and R 2 alkyl groups).
- such oligomers, polymers, copolymers, and other compounds having formula 23 in which Q 6 has formula 34 display no or substantially no liquid crystalline phases. In certain embodiments, they are amorphous; and in certain other embodiments, they are crystalline.
- oligomers, polymers, copolymers, and other compounds having formula 23 in which Q 6 has formula 34 are amorphous, crystalline, liquid crystalline, etc., in certain embodiments, they can have good solubility in organic solvents, such as, for example, tetrahydrofuran, toluene, chlorobenzene, and the like, for example, a degree of solubility in one or more of these or other solvents that permits the casting of thin films using techniques known in the art.
- organic solvents such as, for example, tetrahydrofuran, toluene, chlorobenzene, and the like, for example, a degree of solubility in one or more of these or other solvents that permits the casting of thin films using techniques known in the art.
- oligomers, polymers, copolymers (e.g., block copolymers, condensation copolymers, etc.), and other compounds having formula 23 has focused on those in which Z 1 is bonded into the oligomer, polymer, and copolymer via the alpha positions(s) of the terminal thiophene(s) in Z 1 (i.e., the alpha positions(s) of the terminal thiophene(s) in 24A, 24B, 24C, 24D, 25, 26, 27, 28, 29, or 30), it will be appreciated that compounds of the present invention having formula 23 are meant to include oligomers, polymers, copolymers (e.g., block copolymers, condensation copolymers, etc.) in which Z 1 is bonded into the oligomer, polymer, and copolymer via other groups, such as where Z 1 is bonded into the oligomer, polymer, and copolymer via one or more OfZ 11 S R 1 and R 2 groups.
- Z 1 is bonded into
- formula 23 has focused on those in which Z 1 is bonded into the oligomer, polymer, and copolymer via an aryl moiety (e.g., as in the case where Q 6 is an aryl group), it will be appreciated that compounds of the present invention having formula 23 are meant to include oligomers, polymers, copolymers (e.g., block copolymers, condensation copolymers, etc.) in which Z 1 is bonded into the oligomer, polymer, and copolymer via other moieties.
- Z 1 can be bonded into the oligomer, polymer, and copolymer via other moieties commonly used in conjugated polymers, such as vinylene moieties.
- Z 1 can be incorporated into the main chain of an oligomer, polymer, or copolymer, for example, as in the case where Z 1 is incorporated into the main chain of conjugated or unconjugated polymer (such as a polyester, a polyurethane, a polyether, a polyamide, a polycarbonate, or a polyketone) or as in the case where Z 1 is incorporated into a side chain of a polymer (such as a polyacrylate, a polymethacrylate, or a poly( vinyl ether)).
- conjugated or unconjugated polymer such as a polyester, a polyurethane, a polyether, a polyamide, a polycarbonate, or a polyketone
- Z 1 is incorporated into a side chain of a polymer (such as a polyacrylate, a polymethacrylate, or a poly( vinyl ether)).
- Z 1 can be incorporated into such conjugated or unconjugated polymers via the alpha positions(s) of the terminal thiophene(s) in Z 1 or via other groups, such as via one or more of Z 1? s R 1 and R 2 groups; and it will be appreciated that compounds of the present invention having formula 23 are meant to encompass such conjugated or unconjugated polymers (e.g., conjugated or unconjugated polymers which include one or more Z 1 moieties having formulae 24C, 24D, 25, 26, 27, 28, 29, or 30).
- Compounds of the present invention having formula 23 are also meant to include monomelic compounds in which at least one of Q 5 and Q 6 is or contains a reactive group that permits and/or facilitates the monomelic compound to be incorporated into a polymer (e.g., as in the case where at least one of Q 5 and Q 6 is an acyl chloride; an alcohol; an acrylate; an amine; a vinyl ether; an alkyl group substituted with an acyl chloride, an alcohol, an acrylate, an amine, a vinyl ether, etc.; an aryl group substituted with an acyl chloride, an alcohol, an acrylate, an amine, a vinyl ether, etc.; and the like).
- a polymer e.g., as in the case where at least one of Q 5 and Q 6 is an acyl chloride; an alcohol; an acrylate; an amine; a vinyl ether; an alkyl group substituted with an acyl chloride, an alcohol, an acrylate
- Compounds of the present invention having formula 23 are also meant to include monomelic compounds in which at least one of R 1 and R 2 contains a reactive group that permits and/or facilitates the monomelic compound to be incorporated into a polymer (e.g., as in the case where at least one of R 1 and R 2 is an alkyl or aryl group substituted with or otherwise containing an acyl chloride, an alcohol, an acrylate, an amine, a vinyl ether, etc.).
- - 47 Attorney Docket No. SP08-086PCT
- T can be S or SO 2 .
- the oxidized compounds of the present invention having formula 23 (i.e., those in which at least some of the Ts are SO 2 ) can be prepared by oxidation, for example, with a peracid, such as 3-chloroperoxybenzoic acid (MCPBA).
- MCPBA 3-chloroperoxybenzoic acid
- Oxidation is generally selective at the central-most rings of the polycyclic fused thiophene ring systems; however, it is contemplated that any of the sulfur atoms in the fused thiophenes can be oxidized. It is also contemplated that oxidation can be carried out at any suitable stage.
- oxidation can be carried out on compounds of formula 23 that have terminal thiophene rings bearing a free carboxylic acid in the alpha position, that have terminal thiophene rings bearing hydrogen in the alpha position, that have terminal thiophene rings bearing a halogen in the alpha position, or that have been incorporated into an oligomer or polymer.
- Compounds of formula 23 can be used in a variety of applications, for example, in a wide variety of devices, such as electronic, optoelectronic, and nonlinear optical devices.
- devices such as electronic, optoelectronic, and nonlinear optical devices.
- devices include field effect transistors (FETs), thin- film transistors (TFTs), organic light-emitting diodes (OLEDs), polymer light-emitting diodes (PLEDs), electro-optic (EO) devices, RFID tags, electroluminescent devices (such as those found in flat panel displays), photovoltaic devices, chemical or biological sensors, laser frequency converters, optical interferometric waveguide gates, wideband electrooptical guided wave analog-to-digital converters, optical parametric devices, and devices described in U.S. Patent Nos.
- monomers, oligomers, polymers, and other compounds of formula 23 can be used as conductive materials, as optical waveguides, as two photon mixing materials, as organic semiconductors, and/or as non-linear optical (NLO) materials.
- NLO non-linear optical
- donor-acceptor chromophore compounds of formula 23 can be used in optical waveguides for laser modulation and deflection, information control in optical circuitry, as well as in numerous other waveguide applications.
- the optical waveguides can be used in a variety of optical devices, such as laser frequency converters, optical interferometric waveguide gates, wideband electrooptical guided wave analog-to-digital converters, optical parametric devices, and - 48 - Attorney Docket No. SP08-086PCT
- optical waveguides include those which comprise a thin film medium having one of the following formulae 101, 102, and 103:
- P 1 and P 2 are polymer main chain units, which can be the same mer unit or different mer unit; C is a comonomer unit where u is an integer greater than zero and v is 0 or an integer greater than zero; S 1 and S 2 are pendant spacer groups having a linear chain length of between about 2-12 atoms; and M is a donor-acceptor chromophore compound of formula 23.
- M can be a compound of formula 23 in which Q 5 is an electron donor and in which Q 6 is an electron acceptor and in which M is bonded to spacer S via the beta substituent(s) on the terminal thiophene ring(s), e.g., via R 1 and/or R 2 .
- Pendant spacer groups, S 1 and S 2 that can be employed include those described in, for example, U.S. Patent Nos. 5,044,725, 4,795,664, 5,247,042, 5,196,509, 4,810,338, 4,936,645, 4,767,169, 5,326,661, 5,187,234, 5,170,461, 5,133,037, 5,106,211, and 5,006,285, which are hereby incorporated by reference.
- Polymers and copolymers, P 1 , P 2 , and C, that can be employed include those that are described in, for example, U.S. Patent Nos. 5,044,725, 4,795,664, 5,247,042, 5,196,509, 4,810,338, 4,936,645, 4,767,169, 5,326,661, 5,187,234, 5,170,461, 5,133,037, 5,106,211, and 5,006,285, which are hereby incorporated by reference.
- the polymers are homopolymers.
- the polymers are copolymers.
- polymers and copolymers examples include acrylate, vinyl carboxylate, substituted arylvinyl, vinyl halide, vinyl carboxylate, alkene, alkadiene, arylvinyl, - 49 - Attorney Docket No. SP08-086PCT
- the polymers comprise an external field-induced orientation and alignment of pendant side chains
- the polymer main chain is a structural type such as polyvinyl, polyoxyalkylene, polysiloxane, polycondensation, and the like.
- the polymer can be applied to a supporting substrate by conventional methods, such as spin coating, dip coating, spraying, Langmuir-Blodgett deposition, and the like.
- the thin film optical waveguide medium after fabrication can be subjected to an external field to orient and align uniaxially the polymer side chains, hi one method, the polymer medium is heated close to or above the polymer glass transition temperature T g , then an external field (e.g., a DC electric field) is applied to the medium of mobile chromophore molecules to induce uniaxial molecular alignment of the chromophore polymer side chains or guests in a guest-host system parallel to the applied field, and the medium is cooled while maintaining the external field effect.
- an external field e.g., a DC electric field
- R 12 , R 13 , and R 14 are independently selected from alkyl and aryl.
- Q 10 and Q 11 are the same.
- Q 10 and Q 11 are the same, and R 12 , R 13 , and R 14 are the same.
- R 12 , R 13 , and R 14 are alkyl, such as where R 12 , R 13 , and R 14 are the same or different C2 to C6 alkyl, where R 12 , R 13 , and R 14 are the same or different C3 or C4 alkyl, and/or where R 12 , R 13 , and R 14 are butyl.
- the compound has either formula 37 or formula 38.
- the compound has either formula 39 or formula 40.
- Compounds having formulae 37, 38, 39, or 40 can be prepared by any suitable method, for example, from the corresponding dihalo thiophenes and dihalo thienothiophenes by treatment with an alkyl lithium compound (e.g., butyl lithium), followed by reaction with sulfur, and then with a trialkyl tin halide (e.g., tributyl tin chloride).
- alkyl lithium compound e.g., butyl lithium
- a trialkyl tin halide e.g., tributyl tin chloride
- compounds having formula 37, 38, 39, and 40 can be prepared following the procedures described in Figures 6A, 6B, 6C, and 6D, respectively.
- dihalo thiophene 110 is first reacted with an alkyl lithium compound (e.g., butyl lithium), followed by reaction with sulfur and then with a trialkyl tin halide (e.g., tributyl tin chloride) to produce di(trialkyltin sulfide) thiophene 111;
- dihalo thiophene 112 is first reacted with an alkyl lithium compound (e.g., butyl lithium), followed by reaction with sulfur and then with a trialkyl tin halide (e.g., tributyl tin chloride) to produce di(trialkyltin sulfide) thiophene 113;
- dihalo thienothiophene 114 is first reacted with an alkyl lithium compound (e.g., butyl lithium), followed by reaction with sulfur and then with a trialkyl tin
- the aforementioned compounds of the present invention having formulae 37, 38, 39, or 40 can be used, for example, in the preparation of compounds of the present invention having formulae 14, 15, 16, or 17 (e.g., using the procedures discussed above in relation to Figures 3A and 3B).
- the present invention also relates to a compound having one of the following formulae 41, 42, 43, 44, 45,or 46: - 51 - Attorney Docket No. SP08-086PCT
- R 15 is selected from hydrogen, alkyl, and aryl; wherein Q 12 is selected from hydrogen, a carboxylic acid, a carboxylic acid derivative, an alkyl group, an aryl group, an aldehyde group, an aldehyde derivative, a ketone group, a hydroxyl group, an unsubstituted thiol group, a substituted thiol group, an alkoxy group, an acrylate group, an amino group, a vinyl group, a vinyl ether group, or a halide; and wherein Q 13 has the formula:
- R 15 is a hydrogen, an alkyl group, or an aryl group.
- R 15 can be a variety of substituted or unsubstituted alkyl groups.
- R 15 can be an unsubstituted alkyl group, such as a straight-chain alkyl group (e.g.
- R 15 is an alkyl group at least four carbons in size. In certain embodiments, R 15 is a substituted alkyl group at least four carbons in size.
- R 15 is a substituted alkyl group at least four carbons in size in which substitution of the alkyl group is separated from the fused thiophene ring system by at least two carbons.
- R 15 is an alkyl group substituted with an aryl group, cycloalkyl group, aralkyl group, an alkenyl group, an alkynyl group, an amino - 52 - Attorney Docket No. SP08-086PCT
- substituted alkyl groups include, but are not limited to, 6-hydroxyhexyl and 3-phenylbutyl.
- selection of R 15 here can depend on the end use of the compound.
- Q 12 is a hydrogen.
- Q 12 is an aldehyde group.
- Q 12 is an aldehyde derivative. Examples of aldehyde derivatives include aldehyde protecting groups, such as acetals (e.g., cyclic acetals).
- Q 12 is a carboxylic acid. In certain embodiments, Q 12 is a carboxylic acid derivative.
- carboxylic acid derivatives include carboxylic acid esters (e.g., substituted alkyl esters, unsubstituted alkyl esters, substituted C1-C6 alkyl esters, unsubstituted C1-C6 alkyl esters, substituted aryl esters, unsubstituted aryl esters, etc.); carboxylic acid amides (e.g., unsubstituted amides, monosubstituted amides, disubstituted amides, etc.); acyl halides (e.g., acyl chlorides, etc.); carboxyl protecting groups; and the like.
- Q 12 is a carboxyl protecting group.
- carboxyl protecting groups include esters, thioesters, and oxazolines.
- linear alkyl esters e.g., linear C1-C8 alkyl esters, such as methyl esters, for example, where Q 5 , Q 6 , or both Q 5 and Q 6 are - COOCH 3
- tertiary alkyl esters e.g., tertiary C4-C8 alkyl esters, such as t-butyl esters, for example, where Q 5 , Q 6 , or both.
- Q 5 and Q 6 are -COOC(CH 3 ) 3 ); aralkyl esters (e.g., (C6- C10)aryl-substituted-(Cl-C4)alkyl esters, such as benzyl esters, for example, where Q 5 , Q 6 , or both Q 5 and Q 6 are -COOCH 2 (C 6 H 5 )); and tertiary alkyl thioesters (e.g., tertiary C4-C8 alkyl thioesters, such as t-butyl thioesters, for example, where Q 5 , Q 6 , or both Q 5 and Q 6 are -C(O)SC(CH 3 ) 3 ).
- aralkyl esters e.g., (C6- C10)aryl-substituted-(Cl-C4)alkyl esters, such as benzyl esters, for example, where Q 5 , Q 6 , or both
- Q 5 , Q 6 , or both Q 5 and Q 6 can be an oxazoline moiety, such as a l,3-oxazolin-2-yl moiety, for example, as in the case Q 5 , Q 6 , or both Q 5 and Q 6 have the formula:
- R 10 and R 11 are the same or different and are selected from hydrogen, alkyl (e.g., a substituted or unsubstituted C1-C8 alkyl), and aryl (e.g., a substituted or unsubstituted phenyl) or R 10 and R 1 ⁇ together with the carbon atom to which they are bound, form a ring (e.g., a 4- to 8-membered (such as a 5-membered, 6-membered, etc.) homocyclic or heterocyclic ring).
- alkyl e.g., a substituted or unsubstituted C1-C8 alkyl
- aryl e.g., a substituted or unsubstituted phenyl
- R 10 and R 11 can be the same or different lower alkyl, such as in the case where R 10 and R 11 are the same or different and are selected from a C1-C6 alkyl.
- R 10 and R 11 are the same lower alkyl, for example as in the case where each of R 10 and R 11 is a methyl group, an ethyl group, a n-propyl group, and i-propyl group, etc.
- R 12 , R 13 , and R 14 are the same. In certain embodiments, R 12 , R 13 , and R 14 are alkyl, such as where R 12 , R 13 , and R 14 are the same or different C2 to C6 alkyl, where R 12 , R 13 , and R 14 are the same or different C3 or C4 alkyl, and/or where R 12 , R 13 , and R 14 are butyl.
- the compound has formula 41. In certain embodiments, the compound has formula 42. In certain embodiments, the compound has formula 42. In certain embodiments, the compound has formula 43. In certain embodiments, the compound has formula 44. In certain embodiments, the compound has formula 45. In certain embodiments, the compound has formula 46.
- Compounds having formulae 41, 42, 43, 44, 45,or 46 can be prepared by any suitable method, for example, from the corresponding halo thiophenes, halo thienothiophenes, and halo dithienothiophenes by treatment with an alkyl lithium compound (e.g., butyl lithium), followed by reaction with sulfur, and then with a trialkyl tin halide (e.g., tributyl tin chloride).
- alkyl lithium compound e.g., butyl lithium
- a trialkyl tin halide e.g., tributyl tin chloride
- compounds having formulae 43 and 45 can be prepared from compounds having formulae 11 and 12 using the reaction described above in relation to Figure 6A.
- FIG. 7 A commonly used synthetic method for making larger fused thiophene compounds is illustrated in Figure 7. It involves the use of butyl lithium as a strong base to generate a double anion (122) from a sulfide-coupled bis(thienothiophene) (121). These anions (122) are then oxidized by introducing appropriate oxidative reagents such as CuCl 2 or FeCl 3 to facilitate the ring closure and formation of the fused thiophene compound (123). Typical yields are 10% to 30%. However, there are some problems with this synthetic procedure.
- sulfide-coupled bis(thienothiophene) (121) has four ⁇ -hydrogen atoms (labeled ⁇ and ⁇ '), and all of these hydrogens are believed to have approximately the same reactivity toward strong base. Therefore, when butyl lithium is introduced to the reaction, all four hydrogens can be removed to form anions. This mixture of anions in different positions may lead to a low yield of desired intermediate 122, which may result a low yield of compound 123. Moreover, the sulfide-coupled bis(thienothiophene) (121) usually has poor solubility at low temperature in solvents appropriate for the butyl lithium reaction, and this can further affect the overall yield.
- certain embodiments of the synthetic routes and intermediates described herein may improve the yield of ⁇ -alkyl substituted fused thiophene compounds (such as 123) or other fused thiophenes.
- certain embodiments of the synthetic routes and intermediates described herein may be better (e.g., in terms of yield) for synthesizing larger fused ring thiophenes, e.g., larger than 4 (although it is to be understood that the usefulness of such synthetic routes and intermediates is not limited to fused ring thiophenes of these sizes).
- the use of a carboxy protecting group in the synthetic process prior to carrying out the ring coupling and ring closure steps may act to (i) enhance the reactants solubility and/or (ii) to block anion formation at unwanted reactive sites.
- the overall yield of fused thiophene is improved despite the process having more steps than conventional procedures (e.g., five steps vs. three for conventional procedures).
- the use of certain embodiments of the synthetic routes and intermediates described herein can overcome or otherwise address the solubility limitations of conventional methods.
- Figure 8 sets forth a comparison of prior art methods (described in PCT Patent Application Publication No. WO 2006/031893 and He et al., J. Ore. Chem.. 72(2):444-451 (2007), which are hereby incorporated by reference) and an embodiment of the synthetic routes and intermediates of the present invention.
- one of the key intermediates in the prior art methods is compound 135 that is generated via decarboxylation of compound 134. Although a good yield can be obtained from this reaction, the poor solubility of compound 136 and/or lack of selectivity between reaction sites on compound 137 give a low yield of compound 138.
- the embodiment of the synthetic routes and intermediates of the present invention set forth in Figure 8 can have one or more of the following advantages: (i) the overall yield of the 134 to 139 to 140 to 141 to 142 to 138 five-step sequence of this embodiment of the present invention can be greater than 30%, while the overall yield of the 134 to 135 to 136 to 138 and 134 to 135 to 137 to 138 three-step sequences of the prior method were only on the order of 5% and 15%, respectively; (ii) this embodiment of the present invention can overcome or otherwise address the solubility limitations of the prior method, which can limit the prior method's utility to the preparation of thiophenes with 5 fused rings or fewer; (iii) this embodiment of the present invention makes possible
- the advantages gained in the final purification and/or yield of 138 can more than offset the additional number of steps involved (e.g., because the workup involved in each of the five steps is fairly easy, generally involving only simple washing procedures (and, in some cases, not requiring any workup prior to use in the next step); because the overall yield for the five- step sequence can be more than twice that of the three-step sequences; etc.).
- the reactions set forth in Figure 8 are meant to be illustrative only, and many other chemistries and strategies can be used to effect particular conversions.
- the conversion of 139 to 140 is shown as being carried out using Bu 3 SnSSnBu 3 .
- this conversion can be effected using other chemistries and strategies.
- 140 can be produced by treating 139 with butyl lithium (or another alkyl lithium) to form the corresponding beta anion and reacting the resulting beta anion with (PhSO 2 ) 2 S or another bis(arylsulfonyl)sulfide (e.g., using procedures analogous to those described in PCT Patent Application Publication No. WO 2006/031893 and He et al., J. Ore. Chem.. 72(2):444-451 (2007), which are hereby incorporated by reference).
- the present invention is further illustrated by the following non-limiting examples.
- Figure 8 shows a synthetic scheme for the preparation of a f ⁇ ve-membered fused thiophene 150 using compounds and procedures described hereinabove. Details regarding this synthetic scheme are set forth in the following Example 2-9.
- 3,7-Ditridecyl-heptathienoacene (150) was prepared using the following procedure.
- Compound 158 (3.17 g, 4.2mmol) was mixed with copper powder (0.40 g) in quinoline (80 mL). The mixture was heated to 240-250 °C in a Woods-metal bath until no gas bubbles were detected. The mixture was cooled to room temperature, and hot hexane (400 mL) was added. This mixture was then repeatedly washed with HCl (2N, 4x50 mL). The hexane then was partially evaporated.
- Example 10 60 - Attorney Docket No. SP08-086PCT
Abstract
Description
Claims
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2011502943A JP5624020B2 (en) | 2008-03-31 | 2009-03-30 | Condensed thiophene and its production and use |
EP09727936.8A EP2274310B1 (en) | 2008-03-31 | 2009-03-30 | Fused thiophenes and methods for making and using same |
US12/935,426 US8487114B2 (en) | 2008-03-31 | 2009-03-30 | Fused thiophenes and methods for making and using same |
CN2009801201946A CN102046636A (en) | 2008-03-31 | 2009-03-30 | Fused thiophenes and methods for making and using same |
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Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20070161776A1 (en) * | 2004-09-14 | 2007-07-12 | Mingqian He | Fused thiophenes, methods for making fused thiophenes, and uses thereof |
Family Cites Families (18)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS6239592A (en) * | 1985-08-16 | 1987-02-20 | Sankyo Co Ltd | Tin compound and miticide containing same |
DE4234230C2 (en) | 1992-10-10 | 2003-08-14 | Covion Organic Semiconductors | Substituted thieno [3,2-b] thiophenes and their use |
US5750720A (en) | 1996-03-28 | 1998-05-12 | Ortho Pharmaceutical Corporation | 4- (thien-3-yl)methyl!-imidazole analgesics |
DE69819923T2 (en) * | 1997-09-05 | 2004-09-02 | Cambridge Display Technology Ltd. | CONNECTIONS FOR AN ELECTRONIC ARRANGEMENT |
KR100911136B1 (en) * | 2001-07-09 | 2009-08-06 | 메르크 파텐트 게엠베하 | Reactive thienothiophenes |
DE60205824T2 (en) * | 2001-07-09 | 2006-05-18 | Merck Patent Gmbh | Thienothiophenderivate |
EP1275651B1 (en) | 2001-07-09 | 2005-08-31 | MERCK PATENT GmbH | Thienothiophene derivatives |
EP1275650A3 (en) | 2001-07-09 | 2003-05-02 | MERCK PATENT GmbH | Thienthiophenes with polymerisable group |
ATE461237T1 (en) * | 2001-08-17 | 2010-04-15 | Merck Patent Gmbh | CONJUGATED COPOLYMERS OF DITHIENOTHIOPHENE AND VINYLENE OR ACETYLENE |
EP1284276B1 (en) | 2001-08-17 | 2010-03-17 | MERCK PATENT GmbH | Conjugated copolymers of dithienothiophene with vinylene or acetylene |
DE60302025T2 (en) * | 2002-09-14 | 2006-07-13 | Merck Patent Gmbh | Mono-, oligo- and poly (3-alkynylthiophenes) and their use as charge transport materials |
EP1477504A1 (en) | 2003-05-16 | 2004-11-17 | MERCK PATENT GmbH | Mono-, oligo- and polymers comprising dithienotiophene and aryl groups |
US7244809B2 (en) * | 2003-05-16 | 2007-07-17 | Merck Patent Gmbh | Mono-, oligo- and polymers comprising dithienothiophene and aryl groups |
WO2005087780A1 (en) * | 2004-03-10 | 2005-09-22 | Japan Science And Technology Agency | Chalcogen-containing fused-ring polycyclic organic material and process for producing the same |
KR101209378B1 (en) | 2004-05-18 | 2012-12-06 | 메르크 파텐트 게엠베하 | - - 32-MONO- OLIGO- AND POLYTHIENO32-bTHIOPHENES |
JP2008504370A (en) | 2004-06-09 | 2008-02-14 | メルク パテント ゲゼルシャフト ミット ベシュレンクテル ハフトング | Polymerizable thieno [3,2-b] thiophenes |
EP1778695B1 (en) | 2004-08-21 | 2012-03-21 | Merck Patent GmbH | POLYMERS OF THIENO[2,3-b]THIOPHENE |
CN101111497B (en) | 2004-09-14 | 2013-10-30 | 康宁股份有限公司 | Fused thiophenes, methods for making fused thiophenes, and uses thereof |
-
2009
- 2009-03-30 CN CN2013100203410A patent/CN103122006A/en active Pending
- 2009-03-30 TW TW098110554A patent/TWI391394B/en not_active IP Right Cessation
- 2009-03-30 KR KR1020107024594A patent/KR101652533B1/en active IP Right Grant
- 2009-03-30 CN CN2009801201946A patent/CN102046636A/en active Pending
- 2009-03-30 WO PCT/US2009/001965 patent/WO2009123695A1/en active Application Filing
- 2009-03-30 US US12/935,426 patent/US8487114B2/en not_active Expired - Fee Related
- 2009-03-30 EP EP09727936.8A patent/EP2274310B1/en not_active Not-in-force
- 2009-03-30 JP JP2011502943A patent/JP5624020B2/en not_active Expired - Fee Related
-
2013
- 2013-06-18 US US13/920,502 patent/US8575354B1/en not_active Expired - Fee Related
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20070161776A1 (en) * | 2004-09-14 | 2007-07-12 | Mingqian He | Fused thiophenes, methods for making fused thiophenes, and uses thereof |
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Also Published As
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TWI391394B (en) | 2013-04-01 |
JP2011516474A (en) | 2011-05-26 |
US8575354B1 (en) | 2013-11-05 |
JP5624020B2 (en) | 2014-11-12 |
US20130281707A1 (en) | 2013-10-24 |
US20110098478A1 (en) | 2011-04-28 |
CN102046636A (en) | 2011-05-04 |
KR101652533B1 (en) | 2016-08-30 |
EP2274310B1 (en) | 2016-05-25 |
US8487114B2 (en) | 2013-07-16 |
TW201008947A (en) | 2010-03-01 |
KR20100137555A (en) | 2010-12-30 |
CN103122006A (en) | 2013-05-29 |
EP2274310A1 (en) | 2011-01-19 |
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