U.S. patent application number 13/920502 was filed with the patent office on 2013-10-24 for fused thiophenes and methods for making and using same.
The applicant listed for this patent is Corning Incorporated. Invention is credited to Mingqian He, Thomas Mark Leslie, Feixia Zhang.
Application Number | 20130281707 13/920502 |
Document ID | / |
Family ID | 40791145 |
Filed Date | 2013-10-24 |
United States Patent
Application |
20130281707 |
Kind Code |
A1 |
He; Mingqian ; et
al. |
October 24, 2013 |
FUSED THIOPHENES AND METHODS FOR MAKING AND USING SAME
Abstract
Disclosed are compounds having one of the following formulae:
##STR00001## wherein X is an aromatic nucleophilic substitution
leaving group; R.sup.1 is hydrogen, an alkyl group, or an aryl
group; and Q.sup.1 is a carboxyl protecting group or an aldehyde
protecting group. Also disclosed are fused thiophenes that can be
prepared using these compounds, as well as stannylthio-containing
thiophene, thienothiophene, and dithienothiophene compounds that
can be used to prepare fused thiophenes. Methods for making and
using the aforementioned compounds, fused thiophenes, and
stannylthio-containing thiophene, thienothiophene, and
dithienothiophene compounds are also disclosed.
Inventors: |
He; Mingqian; (Horseheads,
NY) ; Leslie; Thomas Mark; (Horseheads, NY) ;
Zhang; Feixia; (Shanghai, CN) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
Corning Incorporated |
Corning |
NY |
US |
|
|
Family ID: |
40791145 |
Appl. No.: |
13/920502 |
Filed: |
June 18, 2013 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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12935426 |
Dec 13, 2010 |
8487114 |
|
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PCT/US09/01965 |
Mar 30, 2009 |
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13920502 |
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61072468 |
Mar 31, 2008 |
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Current U.S.
Class: |
548/106 ;
549/3 |
Current CPC
Class: |
C07D 495/14 20130101;
C07F 7/2208 20130101; C08G 61/123 20130101; Y02P 20/55 20151101;
H01L 51/0068 20130101; C09K 19/3491 20130101; C07D 495/04 20130101;
C08G 61/126 20130101; C09K 19/40 20130101; C08G 2261/364 20130101;
C07D 495/22 20130101; C08G 2261/3243 20130101 |
Class at
Publication: |
548/106 ;
549/3 |
International
Class: |
H01L 51/00 20060101
H01L051/00 |
Claims
1.-73. (canceled)
74. A compound having one of the following formulae 41, 42, 43, 44,
45,or 46: ##STR00045## wherein R.sup.15 is selected from hydrogen,
alkyl, and aryl; wherein Q.sup.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.sup.13 has the formula: ##STR00046## wherein R.sup.12,
R.sup.13, and R.sup.14 are independently selected from alkyl and
aryl.
75. A compound according to claim 74, wherein Q.sup.12 is a
carboxyl protecting group or an aldehyde protecting group.
76. A compound according to claim 74, wherein Q.sup.12 is an
oxazoline moiety.
77. A compound according to claim 74, wherein Q.sup.12 has the
formula: ##STR00047## wherein R.sup.10 and R.sup.11 are the same or
different and are selected from hydrogen, alkyl, and aryl or
R.sup.10 and R.sup.11, together with the carbon atom to which they
are bound, form a ring.
78. A compound according to claim 77, wherein R.sup.10 and R.sup.11
are the same or different and are lower alkyl.
79. A compound according to claim 77, wherein R.sup.10 is a methyl
group and R.sup.11 is a methyl group.
80. A compound according to claim 74, wherein R.sup.12, R.sup.13,
and R.sup.14 are alkyl.
81. A compound according to claim 74, wherein R.sup.12, R.sup.13,
and R.sup.14 are C2 to C6 alkyl.
82. A compound according to claim 74, wherein R.sup.12, R.sup.13,
and R.sup.14 are C3 or C4 alkyl.
83. A compound according to claim 74 wherein R.sup.12, R.sup.13,
and R.sup.14 are butyl.
Description
CROSS-REFERENCE TO RELATED APPLICATION
[0001] This application claims the benefit of priority to U.S.
provisional application No. 61/072,468, filed on Mar. 31, 2008 and
entitled "Fused Thiophene and Methods for Making and Using Same,"
the content of which is incorporated by reference herein in its
entirety.
TECHNICAL FIELD
[0002] The present invention relates, generally, to heterocyclic
organic compounds and, more particularly, to fused thiophene
compounds and to methods for making and using same.
BACKGROUND
[0003] 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. 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.
[0004] Materials such as pentacene, poly(thiophene),
poly(thiophene-co-vinylene), poly(p-phenylene-co-vinylene) and
oligo(3-hexylthiophene) have been intensively studied for use in
various electronic and optoelectronic applications. More recently,
fused thiophene compounds have been found to have advantageous
properties. For example, bisdithieno[3,2-b:2',3'-d]thiophene (1,
j=2) has been found to efficiently .pi.-stack in the solid state,
to have a high mobility (up to 0.05 cm.sup.2/Vs), and to have a
high on/off ratio (up to 10.sup.8). Oligomers and polymers of fused
thiophenes, such as oligo- or poly(thieno[3,2-b]thiophene (2) and
oligo- or poly(dithieno[3,2-b:2'-3'-d]thiophene) (1)
##STR00002##
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.
SUMMARY
[0006] The present invention relates to a compound having one of
the following formulae 11 or 12:
##STR00003##
wherein X is an aromatic nucleophilic substitution leaving group;
R.sup.1 is hydrogen, an alkyl group, or an aryl group; and Q.sup.1
is a carboxyl protecting group or an aldehyde protecting group.
[0007] The present invention also relates to a compound having one
of the following formulae 14, 15, 16, or 17:
##STR00004##
wherein R.sup.1 and R.sup.2 are the same or different and are
selected from hydrogen, alkyl, and aryl; Q.sup.3 and Q.sup.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.sup.2 has one of the
following formulae 18, 19, 20, 21A, or 21B:
##STR00005##
or one of the following formulae 22A, 22B, 22C, 22D, or 22E:
##STR00006##
wherein R.sup.3 and R.sup.4 are the same or different and are
selected from alkyl and aryl.
[0008] The present invention also relates to a compound having the
following formula 23:
Q.sup.5-Z.sup.1-Q.sup.6 23
wherein Z.sup.1 has one of the following formulae wherein Z.sup.1
has one of the following formulae 24A, 24B, 24C, 24D, 25, 26, 27,
28, 29, or 30:
##STR00007## ##STR00008##
wherein n is 3, 4, or 5; m is 2, 3, or 4; G is selected from
--Se--, --Te--, --B(R.sup.3)--, --P(R.sup.3)--, and
--Si(R.sup.3)(R.sup.4)--; each T is independently selected from S
and SO.sub.2; R.sup.1 and R.sup.2 are the same or different and are
selected from hydrogen, alkyl, and aryl; Q.sup.5 and Q.sup.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, provided that, when
Z.sup.1 has formula 24A or 24B, at least one of Q.sup.5 and Q.sup.6
is a thioester, an oxazoline moiety, or an acetal.
[0009] The present invention also relates to a compound having one
of the following formulae 37, 38, 39, or 40:
##STR00009##
wherein Q.sup.10 and Q.sup.11 are the same or different and have
the formula:
##STR00010##
wherein R.sup.12, R.sup.13, and R.sup.14 are independently selected
from alkyl and aryl.
[0010] The present invention also relates to a compound having one
of the following formulae 41, 42, 43, 44, 45,or 46:
##STR00011##
wherein R.sup.15 is selected from hydrogen, alkyl, and aryl;
wherein Q.sup.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.sup.13 has the
formula:
##STR00012##
wherein R.sup.12, R.sup.13, and R.sup.14 are independently selected
from alkyl and aryl.
[0011] These and additional features and embodiments of the present
invention will be more fully illustrated and discussed in the
following drawings and detailed description.
BRIEF DESCRIPTION OF THE DRAWINGS
[0012] FIGS. 1A and 1B are synthetic schemes that can be used to
prepare certain compounds of the present invention.
[0013] FIGS. 2A-2C are synthetic schemes that can be used to
prepare certain compounds of the present invention.
[0014] FIGS. 3A and 3B are synthetic schemes that can be used to
prepare certain compounds of the present invention.
[0015] FIG. 4 is a synthetic scheme that can be used to prepare
certain compounds of the present invention.
[0016] FIG. 5 is a synthetic scheme that can be used to prepare
certain compounds of the present invention.
[0017] FIGS. 6A-6D are synthetic schemes that can be used to
prepare certain compounds of the present invention.
[0018] FIG. 7 is a synthetic scheme showing a prior art method for
preparing fused thiophenes.
[0019] FIGS. 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.
[0020] FIGS. 10 and 11 are synthetic schemes that can be used to
prepare certain compounds of the present invention.
[0021] The embodiments set forth in the figures are illustrative in
nature and not intended to be limiting of the invention defined by
the claims. Individual features of the drawings and the invention
will be more fully discussed in the following detailed
description.
DETAILED DESCRIPTION
[0022] Before the present materials, articles, and/or methods are
disclosed and described, it is to be understood that the aspects
described below are not limited to specific compounds, synthetic
methods, or uses, but is to be understood to be illustrative of the
invention. It is also to be understood that the terminology used
herein is for the purpose of describing particular aspects only and
is not intended to be limiting.
[0023] In this specification and in the claims that follow,
reference will be made to a number of terms that shall be defined
to have the following meanings:
[0024] Throughout this specification and claims, unless the context
requires otherwise, the word "comprise" or variations, such as
"comprises" or "comprising", will be understood to imply the
inclusion of a stated element, integer, or step or group of
elements, integers, or steps but not the exclusion of any other
element, integer, or step or group of elements, integers, or
steps.
[0025] It must be noted that, as used in the specification and the
appended claims, the singular forms "a", "an", and "the" include
plural referents unless the context clearly dictates otherwise.
Thus, for example, reference to "a compound" is meant to include
mixtures of two or more such compounds; reference to "a moiety" is
meant to include mixtures of two or more such moieties; and the
like.
[0026] "Optional" or "optionally" means that the subsequently
described event or circumstance can or cannot occur, and that the
description includes instances where the event or circumstance
occurs and instances where it does not.
[0027] 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.
[0028] A weight percent of a component, unless specifically stated
to the contrary, is based on the total weight of the formulation or
composition in which the component is included.
[0029] The term "alkyl group" as used herein is a saturated
hydrocarbon group of 1 to 40 carbon atoms. As used herein, "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-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl,
2-methyl-2-ethylpropyl, 2-methyl-1-ethylpropyl, and the like; and
lower cycloalkyls (e.g., C3-C8 cycloalkyls), such as cyclopropyl,
cyclobutyl, cyclopentyl, cyclohexyl, and the like. "Alkyl", as use
herein, is meant to include unsubstituted alkyls, such as those set
forth above, in which no atoms other than carbon and hydrogen are
present. "Alkyl", as use herein, 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.
Further, alkyl groups bearing one or more alkenyl or alkynyl
substituents (e.g., a methyl group itself substituted with a
prop-1-en-1-yl group to produce a but-2-en-1-yl substituent) is
meant to be included in the meaning of "alkyl". Other 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). As noted
above, the alkyl group can be substituted or unsubstituted. The
term "unsubstituted alkyl group" is defined herein as an alkyl
group composed of just carbon and hydrogen. The term "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. As
also noted above, the term "alkyl group" as used herein also
includes cycloalkyl groups. The term "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. As indicated above, the term "alkyl
group" as used herein also includes aralkyl groups. The term
"aralkyl" as used herein 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.
[0030] As used herein, "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, 4-methylphenoxy, and the
like.
[0031] As used herein, "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. For example, naphthyl groups, indole
groups, thienothienyl groups, dithienothienyl, and
5,6,7,8-tetrahydro-2-naphthyl groups (each of which can be
optionally substituted) 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.
[0032] As used herein, "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. Furthermore, two
or more ring substituents can combine to form another ring, so that
"ring", as used herein, is meant to include fused ring systems. In
the case where the ring is saturated (i.e., in the case where each
of the atoms making up the ring are joined by single bonds to other
members of the ring), the ring may optionally include unsaturated
(aromatic or nonaromatic) or saturated substituents.
[0033] The term "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.
[0034] The term "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.
[0035] In the specification that follows, compounds, compositions,
methods, and the like, may be disclosed as containing a combination
of components. When combinations of such components are disclosed,
while specific reference to each individual and collective
combination, permutation, or subset of these components may not be
explicitly disclosed, each individual and collective combination,
permutation, and subset is specifically contemplated and is to be
considered as being particularly described herein. For example, if
a class of components A, B, and C are disclosed; and a class of
components D, E, and F are disclosed; and an example of a
combination, A-D, is disclosed, then, even if each combination is
not individually recited, each is individually and collectively
contemplated. Thus, in this example, 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. Likewise, any subset
or combination of these is also specifically contemplated and
disclosed. Thus, for example, 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. This concept applies to all aspects of this disclosure
including, but not limited to, steps in methods of making and using
the disclosed compositions. Thus, if there are a variety of
additional steps that can be performed, it is understood that each
of these additional steps can be performed with any specific
embodiment or combination of embodiments of the disclosed methods,
and that each such combination is specifically contemplated and
should be considered disclosed. By way of further illustration,
this concept applies to mixtures of various compounds or other
components in compositions; combinations of various components in
devices; and the like.
[0036] One aspect of the present invention relates to a compound
having one of the following formulae 11 or 12:
##STR00013##
wherein X is an aromatic nucleophilic substitution leaving group;
R.sup.1 is hydrogen, an alkyl group, or an aryl group; and Q.sup.1
is a carboxyl protecting group or an aldehyde protecting group.
[0037] Examples of carboxyl protecting groups include esters,
thioesters, and oxazolines. Examples of aldehyde protecting groups
include acetals, such as cyclic acetals. As one skilled in the art
will appreciate, 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.
[0038] As particular examples of Q.sup.1, there can be mentioned
linear alkyl esters (e.g., linear C1-C8 alkyl esters, such as
methyl esters, for example, where Q.sup.1 is --COOCH.sub.3);
tertiary alkyl esters (e.g., tertiary C4-C8 alkyl esters, such as
t-butyl esters, for example, where Q.sup.1 is
--COOC(CH.sub.3).sub.3); aralkyl esters (e.g.,
(C6-C10)aryl-substituted-(C1-C4)alkyl esters, such as benzyl
esters, for example, where Q.sup.1 is
--COOCH.sub.2(C.sub.6H.sub.5)); and tertiary alkyl thioesters
(e.g., tertiary C4-C8 alkyl thioesters, such as t-butyl thioesters,
for example, where Q.sup.1 is --C(O)SC(CH.sub.3).sub.3). As noted
above, Q.sup.1 can be an oxazoline moiety, such as a
1,3-oxazolin-2-yl moiety, for example, as in the case where Q.sup.1
has the formula:
##STR00014##
in which R.sup.10 and R.sup.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.sup.10 and R.sup.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). Illustratively, R.sup.10 and R.sup.11 can be the same or
different lower alkyl, such as in the case where R.sup.10 and
R.sup.11 are the same or different and are selected from a C1-C6
alkyl. In certain embodiments, R.sup.10 and R.sup.11 are the same
lower alkyl, for example as in the case where each of R.sup.10 and
R.sup.11 is a methyl group, an ethyl group, a n-propyl group, and
i-propyl group, etc.
[0039] As noted above, X is an aromatic nucleophilic substitution
leaving group. As used in this context, "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. Examples of suitable leaving groups include F, Cl, Br,
I, and sulfonic esters (e.g. tosylate, mesylate, besylate, and
triflate).
[0040] As noted above, R.sup.1 can be a hydrogen, an alkyl group,
or an aryl group. Illustratively, R.sup.1 can be a variety of
substituted or unsubstituted alkyl groups. For example, R.sup.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. sec-butyl, neo-pentyl, 4-methylpentyl), or a
substituted or unsubstituted cycloalkyl group (e.g. cyclopentyl,
cyclohexyl). In certain embodiments, R.sup.1 is an alkyl group at
least four carbons in size. In certain embodiments, R.sup.1 is a
substituted alkyl group at least four carbons in size. In certain
embodiments, R.sup.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. In certain embodiments, R.sup.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). Examples of substituted
alkyl groups include, but are not limited to, 6-hydroxyhexyl and
3-phenylbutyl. The selection of R.sup.1 can depend on the end use
of the compound. The methods described herein permit the synthesis
of fused thiophene moieties having a wide variety of R.sup.1
substituents. Any functionality that might be present on a
substituted alkyl or aryl R.sup.1 group can be protected, for
example, in order to survive subsequent reaction steps.
[0041] The aforementioned compounds having formula 11 or 12 can be
prepared by any suitable method.
[0042] For example, compounds having formula 12 can be prepared
following the procedures described in FIG. 1A. Referring to FIG.
1A, thiophene 50 (e.g., dibromothiophene) can be reacted with an
acid chloride (e.g., acid chloride 51), for example, in the
presence of a Friedel-Crafts compatible Lewis acid, such as a
stoichiometric amount of AlCl.sub.3, to produce ketone 52. Ketone
52 can be converted to thienothiophene ester 54, for example, by
reaction with 2-mercaptoacetate 53 (e.g., in which R.sup.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. 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
1-amino-2-hydroxyalkane 57 (e.g., in which R.sup.10 and R.sup.11
are the same or different and are selected from hydrogen, alkyl,
and aryl or in R.sup.10 and R.sup.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.
[0043] As further illustration, compounds having formula 11 can be
prepared following the procedures described in FIG. 1B. Referring
to FIG. 1B, thienothiophene 60 (e.g., dibromothienothiophene) can
be reacted with an acid chloride (e.g., acid chloride 61), for
example, in the presence of AlCl.sub.3 or other Friedel-Crafts
compatible Lewis acid (e.g., a stoichiometric amount of
AlCl.sub.3), to produce ketone 62. Ketone 62 can be converted to
dithienothiophene ester 64, for example, by reaction with
2-mercaptoacetate 63 (e.g., in which R.sup.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 corresponding acid chloride (using, for example,
thionyl chloride, oxalyl chloride, etc.), followed by reaction of
the acid chloride with 1-amino-2-hydroxyalkane 67 (e.g., in which
R.sup.10 and R.sup.11 are the same or different and are selected
from hydrogen, alkyl, and aryl or in R.sup.10 and R.sup.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.
[0044] It should be noted that the X groups in the beta positions
of thiophene 50 and thienothiophene 60 can be the same or they can
be different. Illustratively, both X moieties can be the same
halogen, as in the case where both X's are Br. Alternatively, 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.
[0045] The aforementioned compounds having formula 11 or 12 can be
used in a variety of synthetic and other procedures, examples of
which will be apparent from the discussion that follows.
[0046] The present invention, in another aspect thereof, relates to
a compound having one of the following formulae 14, 15, 16, or
17:
##STR00015##
wherein R.sup.1 and R.sup.2 are the same or different and are
selected from hydrogen, alkyl, and aryl; Q.sup.3 and Q.sup.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.sup.2 has one of the
following formulae 18, 19, 20, 21A, or 21B:
##STR00016##
or one of the following formulae 22A, 22B, 22C, 22D, or 22E:
##STR00017##
wherein R.sup.3 and R.sup.4 are the same or different and are
selected from alkyl and aryl.
[0047] Illustratively, examples of such compounds include those set
forth below:
##STR00018## ##STR00019## ##STR00020##
[0048] In certain embodiments, Q.sup.3 and Q.sup.4 are the same. In
certain embodiments, Q.sup.3 and Q.sup.4 are different. In certain
embodiments, Q.sup.3, Q.sup.4, or both Q.sup.3 and Q.sup.4 can be
an aldehyde group or an aldehyde derivative. Examples of aldehyde
derivatives include aldehyde protecting groups, such as acetals
(e.g., cyclic acetals). In certain embodiments, Q.sup.3, Q.sup.4,
or both Q.sup.3 and Q.sup.4 can be a carboxylic acid or a
carboxylic acid derivative. Examples of 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. In certain embodiments, Q.sup.3,
Q.sup.4, or both Q.sup.3 and Q.sup.4 can be a carboxyl protecting
group. Examples of carboxyl protecting groups include esters,
thioesters, and oxazolines. As particular examples, there can be
mentioned linear alkyl esters (e.g., linear C1-C8 alkyl esters,
such as methyl esters, for example, where Q.sup.3, Q.sup.4, or both
Q.sup.3 and Q.sup.4 are --COOCH.sub.3); tertiary alkyl esters
(e.g., tertiary C4-C8 alkyl esters, such as t-butyl esters, for
example, where Q.sup.3, Q.sup.4, or both Q.sup.3 and Q.sup.4 are
--COOC(CH.sub.3).sub.3); aralkyl esters (e.g.,
(C6-C10)aryl-substituted-(C1-C4)alkyl esters, such as benzyl
esters, for example, where Q.sup.3, Q.sup.4, or both Q.sup.3 and
Q.sup.4 are --COOCH.sub.2(C.sub.6H.sub.5)); and tertiary alkyl
thioesters (e.g., tertiary C4-C8 alkyl thioesters, such as t-butyl
thioesters, for example, where Q.sup.3, Q.sup.4, or both Q.sup.3
and Q.sup.4 are --C(O)SC(CH.sub.3).sub.3). As noted above, Q.sup.3,
Q.sup.4, or both Q.sup.3 and Q.sup.4 can be an oxazoline moiety,
such as a 1,3-oxazolin-2-yl moiety, for example, as in the case
where Q.sup.3, Q.sup.4, or both Q.sup.3 and Q.sup.4 have the
formula:
##STR00021##
in which R.sup.10 and R.sup.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.sup.10 and R.sup.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). Illustratively, R.sup.10 and R.sup.11 can be the same or
different lower alkyl, such as in the case where R.sup.10 and
R.sup.11 are the same or different and are selected from a C1-C6
alkyl. In certain embodiments, R.sup.10 and R.sup.11 are the same
lower alkyl, for example as in the case where each of R.sup.10 and
R.sup.11 is a methyl group, an ethyl group, a n-propyl group, and
i-propyl group, etc.
[0049] As noted above, R.sup.1 and R.sup.2 can be the same or
different, each being independently selected from a hydrogen, an
alkyl group, or an aryl group. Illustratively, R.sup.1 and/or
R.sup.2 can be a variety of substituted or unsubstituted alkyl
groups. For example, R.sup.1 and/or R.sup.2 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.
sec-butyl, neo-pentyl, 4-methylpentyl), or a substituted or
unsubstituted cycloalkyl group (e.g. cyclopentyl, cyclohexyl). In
certain embodiments, R.sup.1 and/or R.sup.2 is an alkyl group at
least four carbons in size. In certain embodiments, R.sup.1 and/or
R.sup.2 is a substituted alkyl group at least four carbons in size.
In certain embodiments, R.sup.1 and/or R.sup.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. In certain embodiments, R.sup.1 and/or
R.sup.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. Examples of substituted
alkyl groups include, but are not limited to, 6-hydroxyhexyl and
3-phenylbutyl. In certain embodiments, both R.sup.1 and R.sup.2 are
hydrogen atoms. In certain embodiments, R.sup.1 is a hydrogen atom,
and R.sup.2 is an alkyl group, such as one of the alkyl groups
mentioned above. In certain embodiments, R.sup.2 is a hydrogen
atom, and R.sup.1 is an alkyl group, such as one of the alkyl
groups mentioned above. In certain embodiments both R.sup.1 and
R.sup.2 are the same alkyl group. In certain embodiments R.sup.1
represents one alkyl group, R.sup.2 represents a different alkyl
group. As with the selection of R.sup.1 in the context of compounds
having the formula 11 or 12, selection of R.sup.1 and/or R.sup.2
here can depend on the end use of the compound. The methods
described herein permit the synthesis of fused thiophene moieties
having a wide variety of R.sup.1 and R.sup.2 substituents. Any
functionality that might be present on a substituted alkyl or aryl
R.sup.1 or R.sup.2 group can be protected, for example, in order to
survive subsequent reaction steps.
[0050] As noted above, R.sup.3 and R.sup.4 can be the same or
different, and each is independently selected from an alkyl group
or an aryl group. Illustratively, R.sup.1 and/or R.sup.3 can be a
substituted alkyl group, an unsubstituted alkyl group, a
substituted aryl group, or an unsubstituted aryl group. Suitable
examples of R.sup.3 and R.sup.4 groups include those mentioned
above with regard to R.sup.1 and R.sup.2.
[0051] The aforementioned compounds having formulae 14, 15, 16, or
17 can be prepared by any suitable method.
[0052] For example, compounds having formula 14 in which Q.sup.2
has formula 18 can be prepared following the procedures described
in FIG. 2A 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. Referring to FIG. 2A, oxazolinyl
thienothiophenes 58a and 58b (each of which can be separately
prepared in accordance with the procedures described in FIG. 1A)
are reacted with bis(tributyltin) sulfide 70 to produce compound
72. Compounds having formula 15 in which Q.sup.2 has formula 18 can
be prepared following the procedures described in FIG. 2B from
compounds of the present invention having formula 11 and a
bis(trialkyltin) sulfide, such as those mentioned above. Referring
to FIG. 2B, oxazolinyl dithienothiophenes 68a and 68b (each of
which can be separately prepared in accordance with the procedures
described in FIG. 1B) can be reacted with bis(tributyltin) sulfide
70 to produce compound 74. Although the reaction schemes set forth
in FIGS. 2A and 2B describe the use of bis(tributyltin) sulfide 70,
other chemistries can be employed, such as where preparation of 82
from 58a and 58b or preparation of 86 from 68a and 68b is effected
by reaction with butyl lithium (or another alkyl lithium reagent)
followed by reaction of the resulting beta anion with a
bis(arylsulfonyl)sulfide, such as a bis(phenylsulfonyl)sulfide
(e.g., (PhSO.sub.2).sub.2S), for example, using procedures
analogous to those described in PCT Patent Application Publication
No. WO 2006/031893 and He et al., J. Org. Chem., 72(2):444-451
(2007), which are hereby incorporated by reference.
[0053] As further illustration, compounds having formula 16 or 17
in which Q.sup.2 has formula 18 can be prepared following the
procedures described in FIG. 2C from compounds of the present
invention having formula 11 and 12. Referring to FIG. 2C,
oxazolinyl thienothiophene 58a (which can be prepared in accordance
with the procedures described in FIG. 1A) 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 FIG. 1B) to produce compound 78.
[0054] As yet further illustration, compounds having formula 14 in
which Q.sup.2 has formula 19, 20, 21A, or 21B can be prepared
following the procedures described in FIG. 3A 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) thienothiophene. Referring to FIG. 3A, oxazolinyl
thienothiophenes 58a and 58b (each of which can be separately
prepared in accordance with the procedures described in FIG. 1A)
are reacted with di(trialkyltin sulfide) thiophene or
di(trialkyltin sulfide) thienothiophene 80 to produce compound
82.
[0055] As still further illustration, compounds having formula 15
in which Q.sup.2 has formula 19, 20, 21A, or 21B can be prepared
following the procedures described in FIG. 3B 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. Referring to FIG. 3B, oxazolinyl
dithienothiophene 68a and 68b (each of which can be separately
prepared in accordance with the procedures described in FIG. 2A)
are reacted with di(trialkyltin sulfide) thiophene or
di(trialkyltin sulfide) thienothiophene 84 to produce compound
86.
[0056] The reaction schemes set forth in FIGS. 3A and 3B make use
of di(trialkyltin sulfide) thiophene or di(trialkyltin sulfide)
thienothiophene 80 and 84. Preparative schemes for making these
di(trialkyltin sulfide) thiophenes and di(trialkyltin sulfide)
thienothiophene are described below.
[0057] As still further illustration, compounds having formula 14
in which Q.sup.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 FIG. 3A; and
compounds having formula 15 in which Q.sup.2 has formula 22A, 22B,
22C, 22D, or 22E can be prepared from compounds of the present
invention having formula 11 following procedures similar to that
described in FIG. 3B. More particularly, 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 FIG. 1A)) or a compound of the
present invention having formula 11 (e.g., oxazolinyl
dithienothiophene 68a and 68b (each of which can be separately
prepared in accordance with the procedures described in FIG. 1B))
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.sub.2) to produce compounds having formula 14
or 15 in which Q.sup.2 has formula 22A; a tellurium dihalide (e.g.,
TeCl.sub.2) to produce compounds having formula 14 or 15 in which
Q.sup.2 has formula 22B; an alkyl or aryl boron dihalide (e.g.,
R.sup.3BCl.sub.2, in which R.sup.3 is an alkyl or aryl group) to
produce compounds having formula 14 or 15 in which Q.sup.2 has
formula 22C; a dihalo alkyl phosphine or dihalo aryl phosphine
(e.g., R.sup.3PBr.sub.2, in which R.sup.3 is an alkyl or aryl
group) to produce compounds having formula 14 or 15 in which
Q.sup.2 has formula 22D; or a dihalo dialkyl silane, a dihalo
diaryl silane, or a dihalo alkyl aryl silane (e.g., R.sup.3
R.sup.4SiCl.sub.2, in which R.sup.3 and R.sup.4 are the same or
different and represent an alkyl or aryl group) to produce
compounds having formula 14 or 15 in which Q.sup.2 has formula
22E.
[0058] In all of the reaction schemes discussed above (e.g., those
set forth in FIGS. 2A-2C and 3A-3B), 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.sup.3 and Q.sup.4 are an oxazoline groups). As one skilled in the
art will recognize, 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. These 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.sup.3 and Q.sup.4 are hydrogen atoms)
or other functional groups, such as those described above.
[0059] 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.
[0060] The present invention, in another aspect thereof, relates to
a compound having the formula:
Q.sup.5-Z.sup.1-Q.sup.6 23,
wherein Z.sup.1 has one of the following formulae 24A, 24B, 24C,
24D, 25, 26, 27, 28, 29, or 30:
##STR00022## ##STR00023##
wherein n is 3, 4, or 5; m is 2, 3, or 4; G is selected from
--Se--, --Te--, --B(R.sup.3)--, --P(R.sup.3)--, and
--Si(R.sup.3)(R.sup.4)--; each T is independently selected from S
and SO.sub.2; R.sup.1 and R.sup.2 are the same or different and are
selected from hydrogen, alkyl, and aryl; Q.sup.5 and Q.sup.6 are
the same or different and are selected from hydrogen, a carboxylic
acid, a carboxylic acid derivative, an alkyl group, an aldehyde
derivative, an aryl group, an aldehyde group, 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, provided that, when
Z.sup.1 has formula 24A or 24B, at least one of Q.sup.5 and Q.sup.6
is a thioester, an oxazoline moiety, or an acetal.
[0061] Illustratively, examples of compounds of formula 23 in which
Z.sup.1 has formula 24A include those set forth below:
##STR00024##
Illustrative examples of compounds of formula 23 in which Z.sup.1
has formula 24B include those set forth below:
##STR00025##
Illustrative examples of compounds of formula 23 in which Z.sup.1
has formula 24C include those set forth below:
##STR00026##
Illustrative examples of compounds of formula 23 in which Z.sup.1
has formula 24C include those set forth below:
##STR00027##
[0062] As noted above, R.sup.1 and R.sup.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. Illustratively, R.sup.1
and/or R.sup.2 can be a variety of substituted or unsubstituted
alkyl groups. For example, R.sup.1 and/or R.sup.2 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. sec-butyl, neo-pentyl, 4-methylpentyl), or a
substituted or unsubstituted cycloalkyl group (e.g. cyclopentyl,
cyclohexyl). In certain embodiments, R.sup.1 and/or R.sup.2 is an
alkyl group at least four carbons in size. In certain embodiments,
R.sup.1 and/or R.sup.2 is a substituted alkyl group at least four
carbons in size. In certain embodiments, R.sup.1 and/or R.sup.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. In certain
embodiments, R.sup.1 and/or R.sup.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. Examples
of substituted alkyl groups include, but are not limited to,
6-hydroxyhexyl and 3-phenylbutyl. In certain embodiments, both
R.sup.1 and R.sup.2 are hydrogen atoms. In certain embodiments,
R.sup.1 is a hydrogen atom, and R.sup.2 is an alkyl group, such as
one of the alkyl groups mentioned above. In certain embodiments,
R.sup.2 is a hydrogen atom, and R.sup.1 is an alkyl group, such as
one of the alkyl groups mentioned above. In certain embodiments
both R.sup.1 and R.sup.2 are the same alkyl group. In certain
embodiments R.sup.1 represents one alkyl group, R.sup.2 represents
a different alkyl group. As with the selection of R.sup.1 in the
context of compounds having the formula 11 or 12, selection of
R.sup.1 and/or R.sup.2 here can depend on the end use of the
compound. The methods described herein permit the synthesis of
fused thiophene moieties having a wide variety of R.sup.1 and
R.sup.2 substituents, and any functionality that might be present
on a substituted alkyl or aryl R.sup.1 or R.sup.2 group can be
protected, for example, in order to survive subsequent reaction
steps.
[0063] In certain embodiments, each T is S (i.e., a sulfur atom).
In certain embodiments, at least one T is SO.sub.2. In certain
embodiments, at least one of the three or four central-most T's is
SO.sub.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 T's is
SO.sub.2, and the remaining T's are S; and as in the case where 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.sub.2, and the
remaining T's are S.
[0064] In certain embodiments, each T is independently S or
SO.sub.2, where T is SO.sub.2 in at least one of the central-most
rings of the fused thiophene ring system.
[0065] As used herein, the central-most ring of a fused thiophene
ring system having an odd number 2q+1 of fused rings is the
q+1.sup.th 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.sup.th and q+1.sup.th rings from an end of
the ring system. For example, 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, and the central-most ring of
a seven-ring system is the fourth ring.
[0066] In certain embodiments, Z.sup.1 has one of the formulae 24A
or 24B. In such embodiments, at least one of Q.sup.5 and Q.sup.6 is
a thioester, an oxazoline, or an acetal. For example, in certain
such embodiments, each of Q.sup.5 and Q.sup.6 is a thioester or an
oxazoline, and Q.sup.5 and Q.sup.6 are the same. In certain
embodiments, each of Q.sup.5 and Q.sup.6 is an oxazoline, and
Q.sup.5 and Q.sup.6 are the same. In certain embodiments, each of
Q.sup.5 and Q.sup.6 is an acetal, and Q.sup.5 and Q.sup.6 are the
same. In certain embodiments, one of Q.sup.5 and Q.sup.6 is a
thioester, an oxazoline, or an acetal; and the other of Q.sup.5 and
Q.sup.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. In certain embodiments, at least one of Q.sup.5 and
Q.sup.6 is an oxazoline moiety, such as a 1,3-oxazolin-2-yl moiety,
for example, as in the case where at least one of Q.sup.5 and
Q.sup.6 has the formula:
##STR00028##
in which R.sup.10 and R.sup.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.sup.10 and R.sup.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). Illustratively, R.sup.10 and R.sup.11 can be the same or
different lower alkyl, such as in the case where R.sup.10 and
R.sup.11 are the same or different and are selected from a C1-C6
alkyl. In certain embodiments, R.sup.10 and R.sup.11 are the same
lower alkyl, for example as in the case where each of R.sup.10 and
R.sup.11 is a methyl group, an ethyl group, a n-propyl group, and
i-propyl group, etc.
[0067] In certain embodiments, Z.sup.1 has one of the formulae 24C,
24D, 25, 26, 27, 28, 29, or 30. In such embodiments, Q.sup.5 and
Q.sup.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. By
way of illustration, in certain such embodiments, Q.sup.5 and
Q.sup.6 are the same. In certain embodiments, Q.sup.5 and Q.sup.6
are different. In certain embodiments, at least one of Q.sup.5 and
Q.sup.6 is a hydrogen, such as in the case where each of Q.sup.5
and Q.sup.6 is a hydrogen. In certain embodiments, at least one of
Q.sup.5 and Q.sup.6 is an aldehyde group, such as in the case where
each of Q.sup.5 and Q.sup.6 is an aldehyde group. In certain
embodiments, at least one of Q.sup.5 and Q.sup.6 is an aldehyde
derivative, such as in the case where each of Q.sup.5 and Q.sup.6
is an aldehyde derivative. Examples of aldehyde derivatives include
aldehyde protecting groups, such as acetals (e.g., cyclic acetals).
In certain embodiments, at least one of Q.sup.5 and Q.sup.6 is a
carboxylic acid, such as in the case where each of Q.sup.5 and
Q.sup.6 is a carboxylic acid. In certain embodiments, at least one
of Q.sup.5 and Q.sup.6 is a carboxylic acid derivative, such as in
the case where each of Q.sup.5 and Q.sup.6 is a carboxylic acid
derivative. Examples of 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. In certain embodiments, at least
one of Q.sup.5 and Q.sup.6 is a carboxyl protecting group, such as
in the case where each of Q.sup.5 and Q.sup.6 is a carboxyl
protecting group. Examples of carboxyl protecting groups include
esters, thioesters, and oxazolines. As particular examples, there
can be mentioned linear alkyl esters (e.g., linear C1-C8 alkyl
esters, such as methyl esters, for example, where Q.sup.5, Q.sup.6,
or both Q.sup.5 and Q.sup.6 are --COOCH.sub.3); tertiary alkyl
esters (e.g., tertiary C4-C8 alkyl esters, such as t-butyl esters,
for example, where Q.sup.5, Q.sup.6, or both Q.sup.5 and Q.sup.6
are --COOC(CH.sub.3).sub.3); aralkyl esters (e.g.,
(C6-C10)aryl-substituted-(C1-C4)alkyl esters, such as benzyl
esters, for example, where Q.sup.5, Q.sup.6, or both Q.sup.5 and
Q.sup.6 are --COOCH.sub.2(C.sub.6H.sub.5)); and tertiary alkyl
thioesters (e.g., tertiary C4-C8 alkyl thioesters, such as t-butyl
thioesters, for example, where Q.sup.5, Q.sup.6, or both Q.sup.5
and Q.sup.6 are --C(O)SC(CH.sub.3).sub.3). As noted above, Q.sup.5,
Q.sup.6, or both Q.sup.5 and Q.sup.6 can be an oxazoline moiety,
such as a 1,3-oxazolin-2-yl moiety, for example, as in the case
Q.sup.5, Q.sup.6, or both Q.sup.5 and Q.sup.6 have the formula:
##STR00029##
in which R.sup.10 and R.sup.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.sup.10 and R.sup.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). Illustratively, R.sup.10 and R.sup.11 can be the same or
different lower alkyl, such as in the case where R.sup.10 and
R.sup.11 are the same or different and are selected from a C1-C6
alkyl. In certain embodiments, R.sup.10 and R.sup.11 are the same
lower alkyl, for example as in the case where each of R.sup.10 and
R.sup.11 is a methyl group, an ethyl group, a n-propyl group, and
i-propyl group, etc.
[0068] As noted above, when Z.sup.1 has one of the formulae 24C,
24D, 25, 26, 27, 28, 29, or 30, Q.sup.5 and Q.sup.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. By
way of illustration, choice of Q.sup.5 and Q.sup.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. By way of further
illustration, Q.sup.5 and Q.sup.6 can be selected for their ability
to function as electron donors and/or electron acceptors in
donor-acceptor chromophores. For example, Q.sup.5 and Q.sup.6 can
be chosen such that one of Q.sup.5 and Q.sup.6 is an electron
donating group and the other of Q.sup.5 and Q.sup.6 is an electron
accepting group, such as in the case where Q.sup.5 is an electron
donating group and Q.sup.6 is an electron accepting group or as in
the case where Q.sup.6 is an electron donating group and Q.sup.5 is
an electron accepting group. The phrase "electron 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. The
phrase "electron accepting group" (which is sometimes used
synonymously with "electron withdrawing group") refers to
substituents which attract electron density to a compound's
pi-electron system when the compound's electron structure is
polarized by the input of electromagnetic energy. In this manner,
for example, a compound of the present invention can be a
donor-acceptor chromophore, the term "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. Pat. No. 6,584,266 to He et al., U.S. Pat.
No. 6,514,434 to He et al.; U.S. Pat. No. 6,448,416 to He et al.;
U.S. Pat. No. 6,444,830 to He et al.; and U.S. Pat. No. 6,393,190
to He et al., which are hereby incorporated by reference.
[0069] In certain embodiments, Z.sup.1 has one of the formulae 24C,
24D, 25, 26, 27, 28, 29, or 30, and Q.sup.5 and Q.sup.6 are chosen
such that at least one of Q.sup.5 and Q.sup.6 is an aryl group
having the following formula 31:
-Z.sup.2-Q.sup.7 31,
wherein Z.sup.2 has one of formulae 24A, 24B, 24C, 24D, 25, 26, 27,
28, 29, or 30 and wherein Q.sup.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.
[0070] Illustrative of such compounds are those having the
following formula 32:
Q.sup.5-Z.sup.1-Z.sup.2-Q.sup.7 32,
(i) in which Z.sup.1 has one of the formulae 24C, 24D, 25, 26, 27,
28, 29, or 30 and Z.sup.2 has one of formulae 24A or 24B, for
example, compounds having the formulae:
##STR00030##
and (ii) in which Z.sup.1 has one of the formulae 24C, 24D, 25, 26,
27, 28, 29, or 30 and Z.sup.2 has one of formulae 24C, 24D, 25, 26,
27, 28, 29, or 30, for example, compounds having the formulae:
##STR00031##
In the above formulae, R.sup.21, R.sup.22, R.sup.23, and R.sup.24
can be the same, or they can be different; and each is
independently selected from the moieties recited above for R.sup.1
and R.sup.2 (i.e., hydrogen, an alkyl group, or an aryl group), and
each T is independently selected from S and SO.sub.2.
[0071] As will be apparent from the above discussion, Z.sup.1 and
Z.sup.2 can be the same, or Z.sup.1 and Z.sup.2 can be different.
Moreover, in cases where both Q.sup.5 and Q.sup.6 are aryl groups
having formula 31, Q.sup.5 and Q.sup.6 can be the same (e.g., in
cases where Z.sup.2 and Q.sup.7 is the same for each of Q.sup.5 and
Q.sup.6); or Q.sup.5 and Q.sup.6 can be different (e.g., as in the
case where Q.sup.5's Z.sup.2 is different than Q.sup.6's Z.sup.2
and/or where Q.sup.5's Q.sup.7 is different than Q.sup.6's
Q.sup.7).
[0072] In certain embodiments, Q.sup.6 is an aryl group having
formula 31, and Q.sup.5 and Q.sup.7 are selected such that one of
Q.sup.5 and Q.sup.7 is an electron donating group, and the other of
Q.sup.5 and Q.sup.7 is an electron accepting group. In certain
embodiments, Q.sup.5 is an aryl group having formula 31, and
Q.sup.6 and Q.sup.7 are selected such that one of Q.sup.6 and
Q.sup.7 is an electron donating group and the other of Q.sup.6 and
Q.sup.7 is an electron accepting group. In certain embodiments,
both Q.sup.5 and Q.sup.6 are aryl groups having formula 31, for
example, as in the case where the compound has the following
formula 33:
Q.sup.7-Z.sup.2--Z.sup.1--Z.sup.2-Q.sup.7 33,
and the Q.sup.7's are selected such that one Q.sup.7 is an electron
donating group and the other Q.sup.7 is an electron accepting
group.
[0073] In certain embodiments, Z.sup.1 has one of the formulae 24C,
24D, 25, 26, 27, 28, 29, or 30, and Q.sup.5 and Q.sup.6 are chosen
such that at least one of Q.sup.5 and Q.sup.6 is an aryl group
having the following formula 34:
##STR00032##
wherein each Z.sup.3 is independently selected from formulae 24A,
24B, 24C, 24D, 25, 26, 27, 28, 29, and 30; each Z.sup.4 is the same
or different and is an aryl group; Q.sup.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. Illustratively,
aryl groups that can be used as Z.sup.4 in the above formula 34
include aromatic rings that can undergo a Stille reaction. Examples
of suitable Z.sup.4 groups include benzene rings (e.g., a benzene
ring bonded via the 1 and 4 positions); 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). By way of further illustration of suitable
Z.sup.4 groups, there can be mentioned those of the following
formulae:
##STR00033##
[0074] By way of illustration, 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; and 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;
[0075] For example, when x is one, the compound contains only one
unit having the following formula:
##STR00034##
and there is only one p value and one q value. When x is greater
than one, 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).
[0076] When x is one, the compound contains only one unit having
formula 35, and the number of Z.sup.3 units is p. When p is one,
there is only one Z.sup.3 unit. When p is greater than one, there
is more than one Z.sup.3 unit, and these Z.sup.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.sup.4 units is q. When q is one, there is only one Z.sup.4
unit. When q is greater than one, there is more than one Z.sup.4
unit, and these Z.sup.4 units can be the same, or they can be
different.
[0077] When x is greater than one, the compound contains more than
one unit having formula 35, the number of Z.sup.3 units is x
multiplied by p, and these Z.sup.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.sup.4 units is x multiplied by q, and these Z.sup.4 units can
be the same, or they can be different.
[0078] For example, 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:
##STR00035##
examples of which include:
-Z.sup.31--Z.sup.32--Z.sup.33--Z.sup.34--Z.sup.35--Z.sup.36-Q.sup.7,
-Z.sup.31--Z.sup.31--Z.sup.31--Z.sup.31--Z.sup.31Z.sup.31-Q.sup.7,
-Z.sup.31--Z.sup.32--Z.sup.33--Z.sup.31--Z.sup.32--Z.sup.33-Q.sup.7,
-Z.sup.31--Z.sup.32--Z.sup.31--Z.sup.32--Z.sup.31--Z.sup.32-Q.sup.7,
-Z.sup.31--Z.sup.32--Z.sup.33--Z.sup.32--Z.sup.31--Z.sup.34-Q.sup.7,
and
-Z.sup.31--Z.sup.31--Z.sup.32--Z.sup.32--Z.sup.33--Z.sup.33-Q.sup.7,
in which Z.sup.31, Z.sup.32, Z.sup.33, Z.sup.34, Z.sup.35, and
Z.sup.36 are different from one another and selected from formulae
24A, 24B, 24C, 24D, 25, 26, 27, 28, 29, and 30. In certain
embodiments, each q is zero, and each p is one. In certain
embodiments, each q is zero, each p is one, and each Z.sup.3 is the
same.
[0079] As further illustration, 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:
##STR00036##
examples of which include:
-Z.sup.41--Z.sup.41--Z.sup.41--Z.sup.41--Z.sup.41--Z.sup.41-Q.sup.7,
-Z.sup.41--Z.sup.42--Z.sup.43--Z.sup.41--Z.sup.42--Z.sup.43-Q.sup.7,
-Z.sup.41--Z.sup.42--Z.sup.43--Z.sup.44--Z.sup.45--Z.sup.46-Q.sup.7,
-Z.sup.41--Z.sup.42--Z.sup.41--Z.sup.42--Z.sup.41--Z.sup.42-Q.sup.7,
-Z.sup.41--Z.sup.42--Z.sup.43--Z.sup.42--Z.sup.41--Z.sup.44-Q.sup.7,
and
-Z.sup.41--Z.sup.41--Z.sup.42--Z.sup.42--Z.sup.43--Z.sup.43-Q.sup.7,
in which Z.sup.41, Z.sup.42, Z.sup.43, Z.sup.44, Z.sup.45, and
Z.sup.46 are different from one another, each representing a
different aryl group. In certain embodiments, each p is zero, and
each q is one. In certain embodiments, each p is zero, each q is
one, and each Z.sup.4 is the same.
[0080] As still further illustration, 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:
-Z.sup.31--Z.sup.41-Q.sup.7, -Z.sup.41--Z.sup.31-Q.sup.7,
-Z.sup.41--Z.sup.31--Z.sup.31-Q.sup.7,
-Z.sup.41--Z.sup.31--Z.sup.41-Q.sup.7,
-Z.sup.41--Z.sup.31--Z.sup.41--Z.sup.31--Z.sup.41-Q.sup.7,
-Z.sup.41--Z.sup.42--Z.sup.31Q.sup.7,
-Z.sup.41--Z.sup.31--Z.sup.42--Z.sup.31--Z.sup.43--Z.sup.31-Q.sup.7,
-Z.sup.41--Z.sup.31--Z.sup.41--Z.sup.31--Z.sup.41--Z.sup.31-Q.sup.7,
-Z.sup.41--Z.sup.31--Z.sup.32--Z.sup.42--Z.sup.42--Z.sup.33-Q.sup.7,
and
-Z.sup.41--Z.sup.31--Z.sup.41--Z.sup.32--Z.sup.41--Z.sup.32-Q.sup.7,
in which Z.sup.41, Z.sup.42, and Z.sup.43 are different from one
another, each representing a different aryl group and in which
Z.sup.31, Z.sup.32, and Z.sup.33 are different from one another and
selected from formulae 24A, 24B, 24C, 24D, 25, 26, 27, 28, 29, and
30. In certain embodiments, 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.sup.3 is the same, and each Z.sup.4 is the same.
In certain embodiments each q is the same and is an integer greater
than zero, and each p is one. In certain embodiments, 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.sup.3 is the same; and each Z.sup.4 is the
same.
[0081] Examples of compounds having formula 23 in which Z.sup.1 has
one of the following formulae 24C, 24D, 25, 26, 27, 28, 29, or 30
and in which Q.sup.5 and Q.sup.6 are chosen such that at least one
of Q.sup.5 and Q.sup.6 is an aryl group having formula 34 include
those having the formulae set forth below:
##STR00037##
in which R.sup.21, R.sup.22, R.sup.23, and R.sup.24 are the same or
different and each is independently selected from the moieties
recited above for R' and R.sup.2 (i.e., hydrogen, an alkyl group,
or an aryl group); in which each T is independently selected from S
and SO.sub.2; and in which x is an integer greater than zero.
[0082] In certain embodiments, the aforementioned compounds have
formula 23 in which Z.sup.1 has one of the following formulae 24C,
24D, 25, 26, 27, 28, 29, or 30; in which one of Q.sup.5 and Q.sup.6
is an aryl group having formula 34; in which the other of Q.sup.5
and Q.sup.6 is an electron donating group or an electron accepting
group; in which, when the other of Q.sup.5 and Q.sup.6 is an
electron donating group, Q.sup.7 is an electron accepting group;
and in which, when the other of Q.sup.5 and Q.sup.6 is an electron
accepting group, Q.sup.7 is an electron donating group. In one
illustrative example, Q.sup.6 is an aryl group having formula 34;
one of Q.sup.5 and Q.sup.7 is an electron donating group; and the
other of Q.sup.5 and Q.sup.7 is an electron accepting group. In
another illustrative example, Q.sup.5 is an aryl group having
formula 34; one of Q.sup.6 and Q.sup.7 is an electron donating
group; and the other of Q.sup.6 and Q.sup.7 is an electron
accepting group.
[0083] In certain embodiments, the aforementioned compounds have
formula 23 in which Z.sup.1 has one of the following formulae 24C,
24D, 25, 26, 27, 28, 29, or 30; in which one of Q.sup.5 and Q.sup.6
is an aryl group having formula 34; and in which the other of
Q.sup.5 and Q.sup.6 is an aryl group having the formula:
##STR00038##
wherein each Z.sup.5 is independently selected from formulae 24A,
24B, 24C, 24D, 25, 26, 27, 28, 29, and 30; wherein each Z.sup.6 is
the same or different and is an aryl group; wherein one of Q.sup.7
and Q.sup.8 is an electron donating group or an electron accepting
group; wherein, when Q.sup.7 is an electron donating group, Q.sup.8
is an electron accepting group; wherein, when Q.sup.7 is an
electron accepting group, Q.sup.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.
[0084] Compounds of the present invention having formula 23 wherein
Z.sup.1 has one of the formulae 24A, 24B, 24C, 24D, 25, 26, 27, 28,
29, or 30 can be prepared by any suitable method.
[0085] For example, compounds of formula 23 in which Z.sup.1 has
formula 24B wherein m is 2 or in which Z.sup.1 had formula 24C can
be prepared from compounds of the present invention having formula
14 in which Q.sup.2 has formula 18, 22A, 22B, 22C, 22D, or 22E.
Illustratively, compound 72 (e.g., prepared in accordance with the
procedures described in FIG. 2A when Q.sup.2 is S or in accordance
with the procedures described above when Q.sup.2 is --Se--, --Te--,
--B(R.sup.3)--, --P(R.sup.3)--, or --Si(R.sup.3)(R.sup.4)--) can be
treated with an alkyl lithium (e.g., butyl lithium) and a copper
halide (e.g., CuCl.sub.2) or iron salt (e.g., iron acetate) to
produce compound 90, as shown in FIG. 4.
[0086] Compounds of formula 23 in which Z.sup.1 has formula 24A in
which n is 3 can be prepared from compounds having formula 16 or 17
in which Q.sup.2 has formula 18. Illustratively, compound 78 (e.g.,
prepared in accordance with the procedures described in FIG. 2C)
can be treated with an alkyl lithium (e.g., butyl lithium) and a
copper halide (e.g., CuCl.sub.2) or iron salt (e.g., iron acetate)
to produce a compound in which Z.sup.1 has formula 24A in which n
is 3.
[0087] Compounds of formula 23 in which Z.sup.1 has formula 24B
wherein m is 3 or in which Z.sup.1 had formula 24D can be prepared
from compounds having formula 15 in which Q.sup.2 has formula 18,
22A, 22B, 22C, 22D, or 22E. Illustratively, compound 74 (e.g.,
prepared in accordance with the procedures described in FIG. 2B
when Q.sup.2 is S or in accordance with the procedures described
above when Q.sup.2 is --Se--, --Te--, --B(R.sup.3)--,
--P(R.sup.3)--, or --Si(R.sup.3)(R.sup.4)--) can be treated with an
alkyl lithium (e.g., butyl lithium) and a copper halide (e.g.,
CuCl.sub.2) or iron salt (e.g., iron acetate) to produce a compound
of formula 23 in which Z.sup.1 has formula 24B in which n is 3.
[0088] Compounds of formula 23 in which Z.sup.1 has formula 24B in
which m is 3 can alternatively be prepared from compounds having
formula 14 in which Q.sup.2 has formula 19 using an alkyl lithium
(e.g., butyl lithium) and a copper halide (e.g., CuCl.sub.2) or
iron salt (e.g., iron acetate).
[0089] The aforementioned treatment with alkyl lithium (e.g., butyl
lithium) and copper halide (e.g., CuCl.sub.2) or iron salt (e.g.,
iron acetate) can also be used to prepare: (i) compounds of formula
23 in which Z.sup.1 has formula 24B in which m is 4 from compounds
having formula 15 in which Q.sup.2 has formula 19; (ii) compounds
of formula 23 in which Z.sup.1 has formula 24A in which n is 4 from
compounds having formula 14 in which Q.sup.2 has formula 21B; (iii)
compounds of formula 23 in which Z.sup.1 has formula 24A in which n
is 5 from compounds having formula 15 in which Q.sup.2 has formula
21B; (iv) compounds of formula 23 in which Z.sup.1 has formula 25
from compounds having formula 14 in which Q.sup.2 has formula 20;
(v) compounds of formula 23 in which Z.sup.1 has formula 26 from
compounds having formula 16 or 17 in which Q.sup.2 has formula 20;
(vi) compounds of formula 23 in which Z.sup.1 has formula 27 from
compounds having formula 15 in which Q.sup.2 has formula 20; (vii)
compounds of formula 23 in which Z.sup.1 has formula 28 from
compounds having formula 14 in which Q.sup.2 has formula 21A;
(viii) compounds of formula 23 in which Z.sup.1 has formula 29 from
compounds having formula 16 or 17 in which Q.sup.2 has formula 21A;
and (ix) compounds of formula 23 in which Z.sup.1 has formula 30
from compounds having formula 15 in which Q.sup.2 has formula
21A.
[0090] In all of the reactions discussed above, the starting
materials (compounds having formula 14, 15, 16, or 17) can 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.sup.3 and Q.sup.4 are an oxazoline moieties). In such cases, the
treatment with alkyl lithium (e.g., butyl lithium) and copper
halide (e.g., CuCl.sub.2) will generally not affect the oxazoline
moiety, and, thus, compounds of formula 23 will have terminal
thiophene rings bearing an oxazoline moiety in the alpha
position.
[0091] As one skilled in the art will recognize, 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.
[0092] 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.
[0093] For example, 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. A typical reaction sequence is illustrated in FIG. 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).
[0094] As further illustration, 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. 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 having the formula (R.sup.25).sub.3Sn--Ar, wherein Ar
comprises an aryl group and R.sup.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(0) catalyst,
examples of which include Pd(PPh.sub.3).sub.4.
[0095] As still further illustration, 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.sup.6 has formula 31 (e.g., compounds having 32) using iron(III)
compounds, such as FeCl.sub.3 or Fe(acac).sub.3. Alternatively,
such compounds (e.g., compounds having 32) 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.
[0096] As yet further illustration, 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.sup.6 has formula 34 in which q
is zero) using iron(III) compounds, such as FeCl.sub.3 or
Fe(acac).sub.3. Alternatively, such conjugated oligomers or
polymers (e.g., having formula 23 in which Q.sup.6 has formula 34
in which q is zero) can be prepared from compounds of formula 23
having both terminal thiophene rings bearing halogen (e.g., Br) in
the alpha positions using organomagnesium mediated chemistries.
[0097] Similar chemistries can be used to prepare conjugated
oligomers or polymers (e.g., having formula 23 in which Q.sup.6 has
formula 34 in which q is not zero). Illustratively, 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.sup.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.sup.25).sub.3Sn--Z.sup.4--Sn(R.sup.25).sub.3, wherein Z.sup.4
comprises an aryl group and R.sup.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(0) catalyst,
examples of which include Pd(PPh.sub.3).sub.4. FIG. 5 illustrates
one embodiment of this method. Briefly, referring to FIG. 5, a
compound of formula 23 having both terminal thiophene rings bearing
halogen in the alpha positions (i.e., compound 96) (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) is
coupled with distannyl aromatic compound 97) (e.g., a
2,5'-distannyltrimethyl-bithiophene) in the presence of
Pd(PPh.sub.3).sub.4 to produce compound 98. Examples of suitable
Z.sup.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.sup.6 has formula 34. In certain
embodiments, such oligomers, polymers, copolymers, and other
compounds having formula 23 in which Q.sup.6 has formula 34 possess
enhanced packing ability and thermal stability. In 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.sup.1 and R.sup.2
(e.g., by changing the length of R.sup.1 and R.sup.2 alkyl groups).
In certain embodiments, such oligomers, polymers, copolymers, and
other compounds having formula 23 in which Q.sup.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. Irrespective of whether the
aforementioned oligomers, polymers, copolymers, and other compounds
having formula 23 in which Q.sup.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.
[0099] While the above discussion of oligomers, polymers,
copolymers (e.g., block copolymers, condensation copolymers, etc.),
and other compounds having formula 23 has focused on those in which
Z.sup.1 is bonded into the oligomer, polymer, and copolymer via the
alpha positions(s) of the terminal thiophene(s) in Z.sup.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.sup.1 is bonded into the
oligomer, polymer, and copolymer via other groups, such as where
Z.sup.1 is bonded into the oligomer, polymer, and copolymer via one
or more of Z.sup.1's R.sup.1 and R.sup.2 groups.
[0100] Moreover, while the above discussion of oligomers, polymers,
copolymers (e.g., block copolymers, condensation copolymers, etc.),
and other compounds having formula 23 has focused on those in which
Z.sup.1 is bonded into the oligomer, polymer, and copolymer via an
aryl moiety (e.g., as in the case where Q.sup.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.sup.1 is bonded into the oligomer, polymer, and
copolymer via other moieties. For example, Z.sup.1 can be bonded
into the oligomer, polymer, and copolymer via other moieties
commonly used in conjugated polymers, such as vinylene moieties. As
further illustration, Z.sup.1 can be incorporated into the main
chain of an oligomer, polymer, or copolymer, for example, as in the
case where Z.sup.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.sup.1 is incorporated into a
side chain of a polymer (such as a polyacrylate, a
polymethacrylate, or a poly(vinyl ether)). It will be appreciated
that Z.sup.1 can be incorporated into such conjugated or
unconjugated polymers via the alpha positions(s) of the terminal
thiophene(s) in Z.sup.1 or via other groups, such as via one or
more of Z.sup.1's R.sup.1 and R.sup.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.sup.1 moieties having formulae 24C, 24D, 25, 26, 27, 28, 29,
or 30).
[0101] Compounds of the present invention having formula 23 are
also meant to include monomeric compounds in which at least one of
Q.sup.5 and Q.sup.6 is or contains a reactive group that permits
and/or facilitates the monomeric compound to be incorporated into a
polymer (e.g., as in the case where at least one of Q.sup.5 and
Q.sup.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). Compounds of the present
invention having formula 23 are also meant to include monomeric
compounds in which at least one of R.sup.1 and R.sup.2 contains a
reactive group that permits and/or facilitates the monomeric
compound to be incorporated into a polymer (e.g., as in the case
where at least one of R.sup.1 and R.sup.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.).
[0102] As noted above, in compounds of the present invention having
formula 23, T can be S or SO.sub.2. The oxidized compounds of the
present invention having formula 23 (i.e., those in which at least
some of the T's are SO.sub.2) can be prepared by oxidation, for
example, with a peracid, such as 3-chloroperoxybenzoic acid
(MCPBA). 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. Illustratively, 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.
[0103] 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. Examples
of such 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. Pat. Nos. 4,767,169, 4,775,215, 4,795,664, 4,810,338,
4,936,645, 5,006,285, 5,044,725, 5,106,211, 5,133,037, 5,170,461,
5,187,234, 5,196,509, 5,247,042, 5,326,661, and 6,584,266, which
are hereby incorporated by reference. In certain embodiments,
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.
[0104] By way of further illustration 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 those
described in, for example, U.S. Pat. Nos. 5,044,725, 4,795,664,
5,247,042, 5,196,509, 4,810,338, 4,936,645, 4,767,169, 4,775,215,
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. Examples of
such optical waveguides include those which comprise a thin film
medium having one of the following formulae 101, 102, and 103:
##STR00039##
in which P.sup.1 and P.sup.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.sup.1 and S.sup.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.
[0105] By way of illustration, M can be a compound of formula 23 in
which Q.sup.5 is an electron donor and in which Q.sup.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.sup.1
and/or R.sup.2.
[0106] Pendant spacer groups, S.sup.1 and S.sup.2, that can be
employed include those described in, for example, U.S. Pat. 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.
[0107] Polymers and copolymers, P.sup.1, P.sup.2, and C, that can
be employed include those that are described in, for example, U.S.
Pat. 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. In certain embodiments, the polymers are homopolymers.
In certain embodiments, the polymers are copolymers. Examples of
polymers and copolymers include acrylate, vinyl carboxylate,
substituted arylvinyl, vinyl halide, vinyl carboxylate, alkene,
alkadiene, arylvinyl, methacrylate, vinyl chloride, vinyl acetate,
vinyl ether, ethylene, propylene, isobutylene, 1-butene, isoprene,
styrene, and the like. In certain embodiments, the polymers
comprise an external field-induced orientation and alignment of
pendant side chains. In certain embodiments, 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. In one method, the
polymer medium is heated close to or above the polymer glass
transition temperature T.sub.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.
[0108] As noted above, certain aspects of the present invention
(e.g., those discussed above in relation to FIGS. 3A and 3B)
involve the use of di(trialkyltin sulfide) thiophenes and
di(trialkyltin sulfide) thienothiophenes. These compounds, to which
the present invention also relates, are described in greater detail
below.
[0109] The present invention also relates to a compound having one
of the following formulae 37, 38, 39, or 40:
##STR00040##
wherein Q.sup.10 and Q.sup.11 are the same or different and have
the formula:
##STR00041##
wherein R.sup.12, R.sup.13, and R.sup.14 are independently selected
from alkyl and aryl. In certain embodiments, Q.sup.10 and Q.sup.11
are the same. In certain embodiments, Q.sup.10 and Q.sup.11 are the
same, and R.sup.12, R.sup.13, and R.sup.14 are the same. In certain
embodiments, R.sup.12, R.sup.13, and R.sup.14 are alkyl, such as
where R.sup.12, R.sup.13, and R.sup.14 are the same or different C2
to C6 alkyl, where R.sup.12, R.sup.13, and R.sup.14 are the same or
different C3 or C4 alkyl, and/or where R.sup.12, R.sup.13, and
R.sup.14 are butyl. In certain embodiments, the compound has either
formula 37 or formula 38. In certain embodiments, the compound has
either formula 39 or formula 40.
[0110] 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). Illustratively, compounds having formula 37, 38, 39, and
40 can be prepared following the procedures described in FIGS. 6A,
6B, 6C, and 6D, respectively. For example, in FIG. 6A, 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; in FIG. 6B, 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; in FIG. 6C, 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
halide (e.g., tributyl tin chloride) to produce di(trialkyltin
sulfide) thienothiophene 115; and in FIG. 6D, dihalo
thienothiophene 116 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) thienothiophene 117.
[0111] 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 FIGS. 3A and 3B).
[0112] The present invention also relates to a compound having one
of the following formulae 41, 42, 43, 44, 45,or 46:
##STR00042##
wherein R.sup.15 is selected from hydrogen, alkyl, and aryl;
wherein Q.sup.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.sup.13 has the
formula:
##STR00043##
wherein R.sup.12, R.sup.13, and R.sup.14 are independently selected
from alkyl and aryl.
[0113] As noted above, R.sup.15 is a hydrogen, an alkyl group, or
an aryl group. Illustratively, R.sup.15 can be a variety of
substituted or unsubstituted alkyl groups. For example, R.sup.15
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. sec-butyl, neo-pentyl, 4-methylpentyl), or a
substituted or unsubstituted cycloalkyl group (e.g. cyclopentyl,
cyclohexyl). In certain embodiments, R.sup.15 is an alkyl group at
least four carbons in size. In certain embodiments, R.sup.15 is a
substituted alkyl group at least four carbons in size. In certain
embodiments, R.sup.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. In certain embodiments, R.sup.15 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. Examples of substituted alkyl groups include, but are not
limited to, 6-hydroxyhexyl and 3-phenylbutyl. As with the selection
of R.sup.1 in the context of compounds having the formula 11 or 12,
selection of R.sup.15 here can depend on the end use of the
compound. The methods described herein permit the synthesis of
fused thiophene moieties having a wide variety of R.sup.15
substituents, and any functionality that might be present on a
substituted alkyl or aryl R.sup.15 group can be protected, for
example, in order to survive subsequent reaction steps.
[0114] In certain embodiments, Q.sup.12 is a hydrogen. In certain
embodiments, Q.sup.12 is an aldehyde group. In certain embodiments,
Q.sup.12 is an aldehyde derivative. Examples of aldehyde
derivatives include aldehyde protecting groups, such as acetals
(e.g., cyclic acetals). In certain embodiments, Q.sup.12 is a
carboxylic acid. In certain embodiments, Q.sup.12 is a carboxylic
acid derivative. Examples of 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. In certain embodiments, Q.sup.12
is a carboxyl protecting group. Examples of carboxyl protecting
groups include esters, thioesters, and oxazolines. As particular
examples, there can be mentioned linear alkyl esters (e.g., linear
C1-C8 alkyl esters, such as methyl esters, for example, where
Q.sup.5, Q.sup.6, or both Q.sup.5 and Q.sup.6 are --COOCH.sub.3);
tertiary alkyl esters (e.g., tertiary C4-C8 alkyl esters, such as
t-butyl esters, for example, where Q.sup.5, Q.sup.6, or both
Q.sup.5 and Q.sup.6 are --COOC(CH.sub.3).sub.3); aralkyl esters
(e.g., (C6-C10)aryl-substituted-(C1-C4)alkyl esters, such as benzyl
esters, for example, where Q.sup.5, Q.sup.6, or both Q.sup.5 and
Q.sup.6 are --COOCH.sub.2(C.sub.6H.sub.5)); and tertiary alkyl
thioesters (e.g., tertiary C4-C8 alkyl thioesters, such as t-butyl
thioesters, for example, where Q.sup.5, Q.sup.6, or both Q.sup.5
and Q.sup.6 are --C(O)SC(CH.sub.3).sub.3). As noted above, Q.sup.5
, Q.sup.6, or both Q.sup.5 and Q.sup.6 can be an oxazoline moiety,
such as a 1,3-oxazolin-2-yl moiety, for example, as in the case
Q.sup.5, Q.sup.6, or both Q.sup.5 and Q.sup.6 have the formula:
##STR00044##
in which R.sup.10 and R.sup.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.sup.10 and R.sup.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). Illustratively, R.sup.10 and R.sup.11 can be the same or
different lower alkyl, such as in the case where R.sup.10 and
R.sup.11 are the same or different and are selected from a C1-C6
alkyl. In certain embodiments, R.sup.10 and R.sup.11 are the same
lower alkyl, for example as in the case where each of R.sup.10 and
R.sup.11 is a methyl group, an ethyl group, a n-propyl group, and
i-propyl group, etc.
[0115] In certain embodiments, R.sup.12, R.sup.13, and R.sup.14 are
the same. In certain embodiments, R.sup.12, R.sup.13, and R.sup.14
are alkyl, such as where R.sup.12, R.sup.13, and R.sup.14 are the
same or different C2 to C6 alkyl, where R.sup.12, R.sup.13, and
R.sup.14 are the same or different C3 or C4 alkyl, and/or where
R.sup.12, R.sup.13, and R.sup.14 are butyl. In certain embodiments,
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.
[0116] 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).
Illustratively, compounds having formulae 43 and 45 can be prepared
from compounds having formulae 11 and 12 using the reaction
described above in relation to FIG. 6A.
[0117] The aforementioned compounds of the present invention having
formulae 41, 42, 43, 44, 45,or 46 can be used, for example, in the
preparation of compounds of the present invention or other
thiophene-containing compounds as would be apparent to those
skilled in the art, for example, from the discussion presented
above and from the examples which follow.
[0118] Certain embodiments of the compounds and methods described
hereinabove may overcome or otherwise address some or all of the
problems that have been encountered in the synthesis of fused
thiophenes, for example, as described below.
[0119] Most of the previously reported synthetic methods are
limited to unsubstituted fused thiophenes or alkyl substituted
fused thiophene compounds with a small number of fused rings (e.g.
two or three rings) (Mazaki et al., Tetrahedron Lett., 25:3315-3318
(1989); Zhang et al., J. Am. Chem. Soc., 127:10502-10503 (2005);
Xiao et al., J. Am. Chem. Soc., 27:13281-13286 (2005); Sato et al.,
J. Chem. Soc. Perkin Trans. 2, 765-770 (1992); Okamoto et al., Org.
Lett., 23:5301-5304 (2005); Toshihiro et al., Chem. Eur. J.,
13:548-556 (2007); Zhang et al., J. Macromolecules, 37:6306-6315
(2004); Armitage et al., Science & Engineering, 51:771 (2006);
and Meyers et al., J. Org. Chem., 39(18): 2787-2793 (1974), which
are hereby incorporated by reference). A commonly used synthetic
method for making larger fused thiophene compounds is illustrated
in FIG. 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.sub.2 or
FeCl.sub.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. For
example, sulfide-coupled bis(thienothiophene) (121) has four
.alpha.-hydrogen atoms (labeled .alpha. and .alpha.'), 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. It is believed that
certain embodiments of the synthetic routes and intermediates
described herein may improve the yield of .beta.-alkyl substituted
fused thiophene compounds (such as 123) or other fused
thiophenes.
[0120] In particular, 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). For example, in certain embodiments,
the use of a carboxy protecting group (e.g., an oxazoline 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. In certain embodiments, 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). Additionally or alternatively, the use of
certain embodiments of the synthetic routes and intermediates
described herein can overcome or otherwise address the solubility
limitations of conventional methods. These solubility limitations
typically limit the conventional methods' utility to the
preparation of thiophenes with 5 fused rings or fewer in poor
yields. In contrast, using certain embodiments of the synthetic
routes and intermediates described herein can permit the facile
preparation of fused thiophenes having a greater number constituent
fused thiophene rings.
[0121] FIG. 8 sets forth a comparison of prior art methods
(described in PCT Patent Application Publication No. WO 2006/031893
and He et al., J. Org. 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.
Referring to FIG. 8, 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. In this regard, note that the 30% yield set forth
in FIG. 8 for the 137 to 138 conversion is for situations where 137
is soluble (i.e., in cases where 138 has five or fewer rings). In
contrast, the embodiment of the synthetic routes and intermediates
of the present invention set forth in FIG. 8 (134 to 139 to 140 to
141 to 142 to 138) 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 facile
preparation of fused thiophenes containing a greater number of
fused rings; (iv) because of the poor yields of the 136 to 138 and
137 to 138 transformations in the prior method, the purity of the
fused ring thiophene obtained as the final product (138) can be
poor, whereas, in this embodiment of the present invention,
purification of intermediates can be easier (e.g., because of
cleaner and/or higher yield reactions) and the purity of the final
product (138) can be significantly higher; (v) even though this
embodiment of the present invention involves five steps in going
from 134 to 138 vs. three steps in the two prior approaches (134 to
135 to 136 to 138 and 134 to 135 to 137 to 138, 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.). As is the case will all of
the figures of the present application, the reactions set forth in
FIG. 8 are meant to be illustrative only, and many other
chemistries and strategies can be used to effect particular
conversions. For example, in FIG. 8, the conversion of 139 to 140
is shown as being carried out using Bu.sub.3SnSSnBu.sub.3. However,
this conversion can be effected using other chemistries and
strategies. For example, 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.sub.2).sub.2S 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. Org.
Chem., 72(2):444-451 (2007), which are hereby incorporated by
reference).
[0122] The present invention is further illustrated by the
following non-limiting examples.
EXAMPLES
Example 1
[0123] FIG. 8 shows a synthetic scheme for the preparation of a
five-membered fused thiophene 150 using compounds and procedures
described hereinabove. Details regarding this synthetic scheme are
set forth in the following Example 2-9.
Example 2
[0124] 3,4-Dibromothienyl-2-tetradecyl-ketone (152) was prepared
using the following procedure. To a mixture of 3,4-dibromothiophene
(151) (36.30 g, 0.15 mol) and AlCl.sub.3 (46.20 g, 0.345 mol) in
CH.sub.2Cl.sub.2 (400 mL) at 0.degree. C., myristoyl chloride
(38.90 g, 0.16 mol) was added dropwise under a nitrogen stream.
This was stirred for 0.5 hours until no starting materials could be
detected by GC/MS. The mixture was then poured into HCl (500 mL,
6M), and the organic was extracted with hexanes (2.times.300 mL).
The combined organic solution was washed with brine (2.times.150
mL) and water (150 mL). After drying over anhydrous MgSO.sub.4, the
solvent was evaporated. A low melting point solid was collected and
was pure enough to be used without further purification (68.0 g,
100%). Mp: 50-52.degree. C., GC-MS 453[M+], .sup.1H NMR (300 MHz,
CD.sub.2Cl.sub.2) .delta. 7.64(s, 1H), 3.03(t, 2H), 1.71(t,2H),
1.27(m,22H), 0.88(t,3H).
Example 3
[0125] 3-Tridecyl-6-bromo-ethylthieno
[3,2-b]thiophene-2-carboxylate (153) was prepared using the
following procedure. Compound 152 (68.0 g, 0.15 mol) was mixed with
K.sub.2CO.sub.3 (82.80 g, 0.60 mol) and DMF (350 mL) in a three
neck flask equipped with a condenser and addition funnel. To this
mixture, ethyl mercaptoacetate (16.42 mL, 0.15 mol) was added
dropwise at 60-70.degree. C. A catalytic amount of 18-crown-6 (20
mg) was used as catalyst. The mixture was heated at 60-70.degree.
C. overnight until no starting materials were detected by GC/MS.
The mixture then was poured into water (600 mL) and extracted by
ethylacetate (2.times.250 ml). Organic washed by brine (3.times.400
ml) and dried by MgSO.sub.4. After evaporating the solvent, the
brownish crude target was obtained and found to be pure enough for
the next reaction (71.0 g, 100%). GC/MS 473[M+].
Example 4
[0126] 3-Tridecyl-6-bromo-thieno[3,2-b]thiophene-2-carboxylic acid
(154) was prepared using the following procedure. Compound 153
(71.0 g, 0.15 mol) was dissolved into a mixture of THF (400 mL),
methanol (50 mL), and LiOH (72 mL, 10% solution). This mixture was
refluxed overnight and poured into concentrated hydrochloric acid
(300 mL). The acid mixture was then diluted to 1000 mL with water.
Solid was filtrated and washed with water (3.times.500 mL). The
light yellow solid was washed with methanol (300 mL) and dried
under vacuum overnight (46.40 g. 69.5%). Mp: 88-90.degree. C.
.sup.1H NMR (300 MHz, CD.sub.2Cl.sub.2) .delta. 7.55(s, 1H),
3.17(t, 2H), 1.75(t,2H), 1.26(m,20H), 0.87(t,3H).
Example 5
[0127]
2-(3-Tridecyl-6-bromo-thieno[3,2-b]thienyl)-4,4-dimethyl-2-oxazolin-
e (155) was prepared using the following procedure.
3-Tridecyl-6-bromo-thieno[3,2-b]thiophene-2-carboxylic acid (154)
(46.12 g, 0.10 mol) was added to 100 ml of thionyl chloride, and
the mixture was stirred at room temperature for 24 hours. The
excess thionyl chloride was distilled, and the remaining dark oil
was distilled by rotating evaporate to yield 48.46 g (100%) of the
acid chloride. The 48.46 g (0.10 mol) of acid chloride was
dissolved in 100 ml of methylene chloride and added in a dropwise
manner to a magnetically stirred solution of 18.51 g (0.2 mol) of
2-amino-2-methyl-1-propanol in 100 ml of methylene chloride at
0.degree. C. The mixture was stirred at 25.degree. C. for 2 hours.
After evaporating the solvent, the organic was extracted with
ethylacetate (2.times.200 mL). The combined organic solution was
washed with brine (2.times.150 mL) and water (150 mL). After drying
over anhydrous MgSO.sub.4, the solvent was evaporated to give oil
crude product 47.37 g (91.80%) of
N-(2,2-dimethyl-3hydroxypropyl)-3-tridecyl-6-bromo
-thieno[3,2-b]thienylamide. To cyclize the amide, thionyl chloride
(43.67 g, 0.37 mol) was added dropwise with stirring to 43.37 g
(0.092 mol) of the amide. When the vigorous reaction had subsided,
the yellow solution was poured into 150 ml water. Organics were
extracted with ethylacetate (3.times.100 mL). The combined organic
extracts were washed with brine (2.times.100 mL) and water (100
mL). After drying over anhydrous MgSO.sub.4, the target was
purified by silica column chromatography, eluting with 20%
ethylacetate/hexane (43.00 g, 93.85%). Mp: 37-39.degree. C. .sup.1H
NMR (300 MHz, CD.sub.2Cl.sub.2) .delta. 7.39(s, 1H), 4.08(s, 2H),
3.16(t, 2H), 1.26-1.70(m, 28H), 0.86(t, 3H).
Example 6
[0128]
Bis(2-(4,4-dimethyl-2-oxazolyl)-3-tridecyl-thieno[3,2-b]thienyl)sul-
fide (156) was prepared using the following procedure. Compound
(155) (24.25 g, 0.0487 mol) was added to a solution of
bis(tri-n-butyltin)sulfide (15.67 g, 0.0256 mmol) and
Pd(PPh.sub.3).sub.4 (2.25 g, 1.95.times.10.sup.-3 mol) in toluene
(40 mL) under nitrogen. The mixture was placed in a pressure vessel
and heated at 125.degree. C. for 60 hours. After filtration, the
organic solution was diluted with hexane (300 mL) and solid was
precipitated. The solid was re-crystallized from acetone to give
156 (11.5 g, 76.7%). Mp: 67-69.degree. C. .sup.1H NMR (300 MHz,
CD.sub.2Cl.sub.2) .delta. 7.64(s, 2H), 4.08(s, 4H), 3.07(t, 4H),
1.25-1.66(m, 56H), 0.86(t, 6H).
Example 7
[0129] Bis(2-(4,4-dimethyl-2-oxazolyl)-3-tridecyl)-heptathienoacene
(157) was prepared using the following procedure. To a solution of
compound 156 (9.0 g, 10.4 mmol) in THF (100 mL), n-butyllithium
(10.4 mL, 2.50M in hexane, 25.90 mmol) was added dropwise at
0.degree. C. under argon. This mixture was stirred at 0.degree. C.
for 30 minutes and then warmed to room temperature for 2 hours
before cooling it to 0.degree. C. again. Copper (II) chloride (3.50
g) powder was added to the reaction solution. This mixture was
stirred overnight and then poured into water (200 mL). The water
solution was heated to boiling, and the solid was filtered. The
solid was placed in water (200 mL) and heated again. After
filtration, the solid was washed with hot acetone (100 mL) and hot
ethanol (100 mL). The yellow solid was boiled in toluene (400 mL)
and was hot filtered. The solution was cooled to room temperature
to give compound 157 as a yellow solid (6.00 g, 66.6%).
Mp:116-118.degree. C. .sup.1H NMR (300 MHz, CD.sub.2Cl.sub.2)
.delta. 4.34(s, 4H), 3.10(t, 4H), 1.26-1.75(m, 56H), 0.87(t,
6H).
Example 8
[0130] 3,6-ditrideyl-heptathienoacene-2,7-dicarboxylate acid (158)
was prepared using the following procedure. Compound 157 (6.00 g,
6.93 mmol) was mixed with HCl (4N, 10 mL) and THF (50 mL) and
heated to reflux for 30 mins. This mixture was acidified with
concentrated HCl (30 mL). The solid that formed was filtered and
washed with water several times, then washed by acetone
(3.times.100 ml). The solid was dried under vacuum and was not
further purified to give (4.75 g, 90.2%). The compound was not
soluble enough for NMR. Mp: 242-244.degree. C.
Example 9
[0131] 3,7-Ditridecyl-heptathienoacene (150) was prepared using the
following procedure. Compound 158 (3.17 g, 4.2 mmol) was mixed with
copper powder (0.40 g) in quinoline (80 mL). The mixture was heated
to 240-250.degree. 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, 4.times.50 mL). The hexane then was partially
evaporated. The target compound was collected by filtration and
re-crystallized from hexane to afford 150 (1.50 g, 53.5%). Mp:
66-67.degree. C. .sup.1H NMR (300 MHz, C.sub.6D.sub.6) .delta. 7.02
(s, 2H), 2.76(t, 4H), 1.26-1.81(m, 44H), 0.87(t, 6H).
Example 10
[0132] Synthesis of 3,4-bis(tributylstannyl)thiophene (111)
according the scheme of FIG. 6A. To 6.80 g (28.11 mmol) of
3,4-dibromothiophene (110) in 15 mL of dry Et.sub.2O at -78.degree.
C. under N.sub.2 protection, 23.6 mL of 2.5 M n-BuLi (59.02 mmol)
in hexane was added dropwise. The resulting solution was stirred at
-78.degree. C. for 20 minutes. 1.80 g (56.13 mmol) of sulfur
flowers was then added into this solution to form a cloudy
solution. After this solution was stirred at -78.degree. C. for 2
hours, 16.8 mL of Bu.sub.3SnCl (62.30 mmol) was added to it. A
clear solution formed was then refluxed for 12 hours. 150 mL of
CH.sub.2Cl.sub.2 and 100 mL of water were added into this reaction
mixture after it was warmed to room temperature. After this mixture
was stirred for 10 minutes, the organic layer was collected and was
washed with saturated NaHCO.sub.3 solution (60 mL) and brine (50
mL). The organic layer was then collected and dried over anhydrous
Na.sub.2SO.sub.4. Solvents were removed from it to yield an oily
product that was kept at 150.degree. C. in Kugelrohr vacuum for 8
hours to yield compound 111 as an oily residue (4.90 g, 24%).
.sup.1H NMR (300 MHz, CD.sub.2Cl.sub.2): .delta. 7.08 (s, 2H),
1.62-0.83 (m, 54H).
Example 11
[0133] Synthesis of 2,5-bis(tributylstannyl)thiophene (113)
according the scheme of FIG. 6B. To 3.22 g (13.31 mmol) of
2,5-dibromothiophene (112) in 90 mL of dry Et.sub.2O at -78.degree.
C. under N.sub.2 protection, 10.6 mL of 2.5 M n-BuLi (26.5 mmol) in
hexane was added dropwise. The resulting solution was stirred at
-78.degree. C. for 20 minutes. 0.86 g (26.82 mmol) of sulfur
flowers was then added into this solution to form a cloudy
solution. After this solution was stirred at -78.degree. C. for 2
hours, 7.36 mL of Bu.sub.3SnCl (27.29 mmol) was added to it. A
clear solution formed was then refluxed for 12 hours. 150 mL of
hexane and 100 mL of water were added into this reaction mixture
after it was warmed to room temperature. After this mixture was
stirred for 10 minutes, the organic layer was collected and was
washed with saturated NaHCO.sub.3 solution (60 mL) and brine (50
mL). The organic layer was collected and dried over anhydrous
Na.sub.2SO.sub.4. Solvents were removed from it to yield an oily
product of compound 113 that was kept at 150.degree. C. in
Kugelrohr vacuum for 8 hours to yield compound 5 as an oily residue
(4.78 g, 49%). .sup.1H NMR (300 MHz, CD.sub.2Cl.sub.2): .delta.
7.33 (s, 2H), 1.62-0.83 (m, 54H).
Example 12
[0134] Synthesis of
2-(6-(tributyltin)sulfanyl-3-decyl-thieno[3,2-b]thiophen-2-yl)-4,4-dimeth-
yl-4,5-dihydro-oxazole (160) according the scheme of FIGS. 10. To
940 mg (2.1 mmol) of vacuum-dried
2-(6-bromosulfanyl-3-decyl-thieno[3,2-b]thiophen-2-yl)-4,4-dimethyl-4,5-d-
ihydro-oxazole (159) in 10 mL of dry Et.sub.2O at -78.degree. C.
under N.sub.2 protection, 0.83 mL of 2.5 M n-BuLi (2.06 mmol) in
hexane was added dropwise. The resulting solution was stirred at
-78.degree. C. for 20 minutes. 66 mg (2.06 mmol) of sulfur flowers
was then added into this solution to form a cloudy solution. After
this solution was stirred at 0.degree. C. for 40 minutes, 0.61 mL
(2.26 mmol) of Bu.sub.3SnCl was added into it. A clear solution
formed was then refluxed for 6 hours. 60 mL of CH.sub.2Cl.sub.2 and
50 mL of water were added into this reaction mixture after it was
warmed to room temperature. After this mixture was stirred for 10
minutes, the organic solution was collected and was washed with
saturated NH.sub.4Cl solution (2.times.20 mL) and water (50 mL).
The organic layer was collected and dried over anhydrous
Na.sub.2SO.sub.4. Solvents were removed from it and the residue was
crystallized from ethanol and then cooled in the refrigerator to
give 0.91 grams of compound 2 as a wet solid of compound 160 (yield
51%). .sup.1H NMR (300 MHz, CD.sub.2Cl.sub.2): .delta. 7.19 (s,
1H), 4.06 (s, 2H), 3.10 (t, 2H), 1.77-1.07 (m, 55H); HRMS (ESI) m/z
calcd for [C.sub.46H.sub.60S.sub.7+1] 700.27, found 700.26.
Example 13
[0135] Synthesis of
2-(6-(trimethyltin)sulfanyl-3-decyl-thieno[3,2-b]thiophen-2-yl)-4,4-dimet-
hyl-4,5-dihydro-oxazole (161) according the scheme of FIG. 11.
Under N.sub.2 protection, 1.29 mL of 2.5 M n-BuLi (3.23 mmol) in
hexane was added dropwise to a solution of
2-(6-bromosulfanyl-3-decyl-thieno[3,2-b]thiophen-2-yl)-4,4-dimethyl-4,5-d-
ihydro-oxazole (159) (1.34 g, 2.94 mmol) in 10 mL of dry Et.sub.2O
at -78.degree. C. After this resulting solution was stirred at
-78.degree. C. for one hour, 94 mg (2.93 mmol) of sulfur flowers
was added into this solution to form a cloudy solution. After this
solution was stirred at 0.degree. C. for 40 minutes, a solution of
of 1 M Me.sub.3SnCl (3.23 mL, 3.23 mmol) in THF was added. A clear
solution formed was refluxed for 6 hours. 60 mL of CH.sub.2Cl.sub.2
and 50 mL of water were added into this reaction mixture after it
was warmed to room temperature. After this mixture was stirred for
10 minutes, the organic layer was collected and was washed with
saturated NaHCO.sub.3 solution (2.times.20 mL) and brine (50 mL).
The organic layer was collected and dried over anhydrous
Na.sub.2SO.sub.4. Solvents were removed from it to form a wet solid
that was crystallized from methanol and then cooled in the
refrigerator to give 1.27 grams of compound 161 as a solid. HRMS
(ESI) m/z calcd for [C.sub.46H.sub.60S.sub.7+1] 574.12, found
574.11.
[0136] Although preferred embodiments have been depicted and
described in detail herein, it will be apparent to those skilled in
the relevant art that various modifications, additions,
substitutions and the like can be made without departing from the
spirit of the invention and these are therefore considered to be
within the scope of the invention, as defined in the claims which
follow.
* * * * *