Organic dye for a dye-sensitized solar cell
09660196 ยท 2017-05-23
Assignee
Inventors
- Alessandro Abbotto (Milan, IT)
- Maurizio Filippo Acciarri (Milan, IT)
- Paolo Biagini (San Giuliano Terme, IT)
- Simona Olga Binetti (Milan, IT)
Cpc classification
C09B57/008
CHEMISTRY; METALLURGY
C07D333/24
CHEMISTRY; METALLURGY
H10K30/15
ELECTRICITY
Y02E10/542
GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
H10K85/636
ELECTRICITY
C07D519/00
CHEMISTRY; METALLURGY
H01G9/2059
ELECTRICITY
H01G9/2004
ELECTRICITY
Y02E10/549
GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
H10K85/6576
ELECTRICITY
International classification
C07D519/00
CHEMISTRY; METALLURGY
C07D333/24
CHEMISTRY; METALLURGY
C09B23/10
CHEMISTRY; METALLURGY
Abstract
Organic dye for a Dye Sensitized Solar Cell (DSSC) comprising at least one electron donor group and at least two electron acceptor groups, each of said electron acceptor groups being bound to said electron donor group through a -conjugated unit. Said organic dye is particularly useful in a dye sensitized photoelectric transformation element, which, in its turn, can be used in a Dye Sensitized Solar Cell (DSSC).
Claims
1. An organic dye having general formula (I): ##STR00070## wherein: P.sub.1, P.sub.2 and P.sub.3, the same or different, are selected from bivalent heteroaryl groups having the following general formulae (VII), (VIII), (IX), (XII), with the proviso that at least one of P.sub.1, P.sub.2 and P.sub.3, is selected from bivalent heteroaryl groups having general formula (VII): ##STR00071## wherein: R.sub.3 and R.sub.4, the same or different, represent a hydrogen atom; or they represent a halogen atom selected from fluorine, chlorine or bromine; or they are selected from linear or branched C.sub.1-C.sub.20 alkyl groups, saturated or unsaturated, optionally containing heteroatoms, aryl groups optionally substituted, heteroaryl groups optionally substituted, cycloalkyl groups optionally substituted, heterocyclic groups optionally substituted, trialkyl- or triaryl-silyl groups, dialkyl- or diaryl-amine groups, dialkyl- or diaryl phosphinic groups, linear or branched C.sub.1-C.sub.20 alkoxyl groups, saturated or unsaturated, aryloxyl groups optionally substituted, thioalkoxyl or thioaryloxyl groups optionally substituted, cyano groups; Z represents a heteroatom selected from oxygen, sulfur, selenium, tellurium; or it is selected from groups having general formula X(R.sub.5) or from groups having general formula Y(R.sub.6R.sub.7), wherein R.sub.5, R.sub.6 and R.sub.7, have the meanings specified hereunder, X represents a heteroatom selected from nitrogen, phosphorous, arsenic, boron, Y represents a carbon, silicon, or germanium atom; W represents a heteroatom selected from oxygen, sulfur, selenium, tellurium; or it is selected from groups having general formula Y(R.sub.6R.sub.7) wherein R.sub.6 and R.sub.7, have the meanings specified hereunder, Y represents a carbon, silicon, or germanium atom; R.sub.5 represents a hydrogen atom; or it is selected from linear or branched C.sub.1-C.sub.20 alkyl groups, saturated or unsaturated, optionally containing heteroatoms, aryl groups optionally substituted, cycloalkyl groups optionally substituted; R.sub.6 and R.sub.7, the same or different, are selected from linear or branched C.sub.1-C.sub.20 alkyl groups, saturated or unsaturated, optionally containing heteroatoms, aryl groups optionally substituted, cycloalkyl groups optionally substituted, linear or branched C.sub.1-C.sub.20 alkoxyl groups, saturated or unsaturated, aryloxyl groups optionally substituted, thioalkoxyl or thioaryloxyl groups optionally substituted; or R.sub.3 and R.sub.4, in general formulae (VIII) or (IX), can be optionally bound to each other so as to form, together with the other atoms to which they are bound, a cycle containing from 1 to 12 carbon atoms, saturated, unsaturated, or aromatic, optionally substituted with linear or branched C.sub.1-C.sub.20 alkyl groups, saturated or unsaturated, optionally containing heteroatoms, aryl groups optionally substituted, heteroaryl groups optionally substituted, cycloalkyl groups optionally substituted, heterocyclic groups optionally substituted, trialkyl- or triaryl-silyl groups, dialkyl- or diaryl-amine groups, dialkyl- or diaryl phosphinic groups, linear or branched C.sub.1-C.sub.20 alkoxyl groups, saturated or unsaturated, aryloxyl groups optionally substituted, thioalkoxyl or thioaryloxyl groups optionally substituted, cyano groups, said cycle optionally containing heteroatoms selected from oxygen, sulfur, nitrogen, silicon, phosphorous, selenium; m, r and s, the same or different, are an integer ranging from 0 to 5, with the proviso that at least one of m, r and s is different from 0, and that at least one of m, r and s is different from 0 for said at least one of P.sub.1, P.sub.2 and P.sub.3 that is selected from bivalent heteroaryl groups having general formula (VII); A represents a group COOH; a phosphonic group having formula PO(OH).sub.2 or PO(OH)(R), wherein R is selected from linear or branched C.sub.1-C.sub.20 alkyl groups; a carboxycyanovinylene group having general formula (XIII) or (XIV): ##STR00072## wherein R.sub.8, R.sub.9 and R.sub.10, the same or different, represent a hydrogen atom; or they represent a halogen atom selected from fluorine, chlorine or bromine; or they are selected from linear or branched C.sub.1-C.sub.20 alkyl groups, saturated or unsaturated, optionally containing heteroatoms, aryl groups optionally substituted, heteroaryl groups optionally substituted, cycloalkyl groups optionally substituted, cyano groups, nitro groups; t is an integer ranging from 2 to 6; D represents a triarylamine group having the following general formulae (XV), (XVI), (XVII), (XVIII), (XIX), (XX), (XXI), (XXII), (XXIII), (XXIV): ##STR00073## ##STR00074## ##STR00075## wherein R.sub.11 represents an hydrogen atom or it is selected from polyethyleneoxyl groups having formula RO[CH.sub.2CH.sub.2O].sub.q wherein R represents a hydrogen atom; or it is selected from linear or branched C.sub.1-C.sub.20 alkyl groups, and q is an integer ranging from 1 to 20, heteroaryl groups optionally substituted.
2. A dye-sensitized photoelectric transformation element, comprising at least one organic dye having general formula (I) according to claim 1, said dye-sensitized photoelectric transformation element being supported on particles of a semiconductor oxide.
3. A Dye-Sensitized Solar Cell (DSSC) comprising the dye-sensitized photoelectric transformation element according to claim 2.
4. An organic dye having general formula (I): ##STR00076## wherein: P.sub.1, P.sub.2 and P.sub.3, the same or different, are selected from bivalent heteroaryl groups having the following general formulae (VII), (VIII), (IX), (XII), with the proviso that at least one of P.sub.1, P.sub.2 and P.sub.3, is selected from bivalent heteroaryl groups having general formula (VII): ##STR00077## wherein: R.sub.3 and R.sub.4, the same or different, represent a hydrogen atom; or they represent a halogen atom selected from fluorine, chlorine or bromine; or they are selected from linear or branched C.sub.1-C.sub.20 alkyl groups, saturated or unsaturated, optionally containing heteroatoms, aryl groups optionally substituted, heteroaryl groups optionally substituted, cycloalkyl groups optionally substituted, heterocyclic groups optionally substituted, trialkyl- or triaryl-silyl groups, dialkyl- or diaryl-amine groups, dialkyl- or diaryl phosphinic groups, linear or branched C.sub.1-C.sub.20 alkoxyl groups, saturated or unsaturated, aryloxyl groups optionally substituted, thioalkoxyl or thioaryloxyl groups optionally substituted, cyano groups; Z represents a heteroatom selected from oxygen, sulfur, selenium, tellurium; or it is selected from groups having general formula X(R.sub.5) or from groups having general formula Y(R.sub.6R.sub.7), wherein R.sub.5, R.sup.6 and R.sub.7, have the meanings specified hereunder, X represents a heteroatom selected from nitrogen, phosphorous, arsenic, boron, Y represents a carbon, silicon, or germanium atom; W represents a heteroatom selected from oxygen, sulfur, selenium, tellurium; or it is selected from groups having general formula Y(R.sub.6R.sub.7) wherein R.sub.6 and R.sub.7, have the meanings specified hereunder, Y represents a carbon, silicon, or germanium atom; R.sub.5 represents a hydrogen atom; or it is selected from linear or branched C.sub.1-C.sub.20 alkyl groups, saturated or unsaturated, optionally containing heteroatoms, aryl groups optionally substituted, cycloalkyl groups optionally substituted; R.sub.6 and R.sub.7, the same or different, are selected from linear or branched C.sub.1-C.sub.20 alkyl groups, saturated or unsaturated, optionally containing heteroatoms, aryl groups optionally substituted, cycloalkyl groups optionally substituted, linear or branched C.sub.1-C.sub.20 alkoxyl groups, saturated or unsaturated, aryloxyl groups optionally substituted, thioalkoxyl or thioaryloxyl groups optionally substituted; or R.sub.3 and R.sub.4, in general formulae (VIII) or (IX), can be optionally bound to each other so as to form, together with the other atoms to which they are bound, a cycle containing from 1 to 12 carbon atoms, saturated, unsaturated, or aromatic, optionally substituted with linear or branched C.sub.1-C.sub.20 alkyl groups, saturated or unsaturated, optionally containing heteroatoms, aryl groups optionally substituted, heteroaryl groups optionally substituted, cycloalkyl groups optionally substituted, heterocyclic groups optionally substituted, trialkyl- or triaryl-silyl groups, dialkyl- or diaryl-amine groups, dialkyl- or diaryl phosphinic groups, linear or branched C.sub.1-C.sub.20 alkoxyl groups, saturated or unsaturated, aryloxyl groups optionally substituted, thioalkoxyl or thioaryloxyl groups optionally substituted, cyano groups, said cycle optionally containing heteroatoms selected from oxygen, sulfur, nitrogen, silicon, phosphorous, selenium; m, r and s, the same or different, are an integer ranging from 0 to 5, with the proviso that at least one of m, r and s is different from 0, and that at least one of m, r and s is different from 0 for said at least one of P.sub.1, P.sub.2 and P.sub.3 that is selected from bivalent heteroaryl groups having general formula (VII); A represents a carboxycyanovinylene group having general formula (XIII): ##STR00078## wherein R.sub.8 represents a hydrogen atom; t is 2; D represents a triarylamine group having general formula (XV): ##STR00079## wherein R.sub.11 represents an hydrogen atom; or it is selected from polyethyleneoxyl groups having formula RO[CH.sub.2CH.sub.2O].sub.q wherein R represents a hydrogen atom; or it is selected from linear or branched C.sub.1-C.sub.20 alkyl groups, and q is an integer ranging from 1 to 20; or R is an aryl group optionally substituted with one or more groups, the same or different, selected from: C.sub.1-C.sub.16 alkyl groups, C.sub.1-C.sub.16 alkoxyl groups, C.sub.1-C.sub.16 thioalkoxyl groups, C.sub.3-C.sub.24 tri-alkylsilyl groups, polyethyleneoxyl groups, amino groups, C.sub.1-C.sub.16 mono- or di-alkylamine groups; or R is a heteroaryl group containing from 1 to 4 heteroatoms selected from nitrogen, oxygen, sulfur, silicon, selenium, phosphorous, optionally substituted with one or more groups, the same or different, selected from C.sub.1-C.sub.16 alkyl groups, C.sub.1-C.sub.16 alkoxyl groups, C.sub.1-C.sub.16 thioalkoxyl groups, C.sub.3-C.sub.24 tri-alkylsilyl groups, polyethyleneoxyl groups, amino groups, C.sub.1-C.sub.16 mono- or di-alkylamine groups.
5. A dye-sensitized photoelectric transformation element, comprising at least one organic dye having general formula (I) according to claim 4, said dye-sensitized photoelectric transformation element being supported on particles of a semiconductor oxide.
6. A Dye-Sensitized Solar Cell (DSSC) comprising the dye-sensitized photoelectric transformation element according to claim 5.
7. An organic dye having general formula (I): ##STR00080## wherein: P represents one of the following general formulae (Ia), (lb), (Ic), (Id):
(T).sub.n-(P.sub.1).sub.m(P.sub.2).sub.r(P.sub.3).sub.s(Ia)
(P.sub.1).sub.m-(T).sub.n-(P.sub.2).sub.r(P.sub.3).sub.s(Ib)
(P.sub.1).sub.m(P.sub.2).sub.r-(T).sub.n-(P.sub.3).sub.s(Ic)
(P.sub.1).sub.m(P.sub.2).sub.r(P.sub.3).sub.s-(T).sub.n-(Id) wherein: T represents a triple carbon-carbon bond having formula (II), or a double carbon-carbon bond having general formula (III) or (IV): ##STR00081## wherein R.sub.1 and R.sub.2, the same or different, represent a hydrogen atom; or they are selected from linear or branched C.sub.1-C.sub.20 alkyl groups, saturated or unsaturated, optionally containing heteroatoms, aryl groups optionally substituted, heteroaryl groups optionally substituted, cycloalkyl groups optionally substituted; n is an integer ranging from 0 to 5; P.sub.1, P.sub.2 and P.sub.3, the same or different, are selected from bivalent heteroaryl groups having the following general formulae (VIII), (IX), (XII), with the proviso that at least one of P.sub.1, P.sub.2 and P.sub.3, is selected from bivalent heteroaryl groups having general formula (VIII) or (IX): ##STR00082## wherein: R.sub.3 and R.sub.4, the same or different, represent a hydrogen atom; or they represent a halogen atom selected from fluorine, chlorine or bromine; or they are selected from linear or branched C.sub.1-C.sub.20 alkyl groups, saturated or unsaturated, optionally containing heteroatoms, aryl groups optionally substituted, heteroaryl groups optionally substituted, cycloalkyl groups optionally substituted, heterocyclic groups optionally substituted, trialkyl- or triaryl-silyl groups, dialkyl- or diaryl-amine groups, dialkyl- or diaryl phosphinic groups, linear or branched C.sub.1-C.sub.20 alkoxyl groups, saturated or unsaturated, aryloxyl groups optionally substituted, thioalkoxyl or thioaryloxyl groups optionally substituted, cyano groups; Z represents a heteroatom selected from oxygen, sulfur, selenium, tellurium; or it is selected from groups having general formula X(R.sub.5) or from groups having general formula Y(R.sub.6R.sub.7), wherein R.sub.5, R.sub.6 and R.sub.7, have the meanings specified hereunder, X represents a heteroatom selected from nitrogen, phosphorous, arsenic, boron, Y represents a carbon, silicon, or germanium atom; W represents a heteroatom selected from oxygen, sulfur, selenium, tellurium; or it is selected from groups having general formula Y(R.sub.6R.sub.7) wherein R.sub.6 and R.sub.7, have the meanings specified hereunder, Y represents a carbon, silicon, or germanium atom; R.sub.5 represents a hydrogen atom; or it is selected from linear or branched C.sub.1-C.sub.20 alkyl groups, saturated or unsaturated, optionally containing heteroatoms, aryl groups optionally substituted, cycloalkyl groups optionally substituted; R.sub.6 and R.sub.7, the same or different, are selected from linear or branched C.sub.1-C.sub.20 alkyl groups, saturated or unsaturated, optionally containing heteroatoms, aryl groups optionally substituted, cycloalkyl groups optionally substituted, linear or branched C.sub.1-C.sub.20 alkoxyl groups, saturated or unsaturated, aryloxyl groups optionally substituted, thioalkoxyl or thioaryloxyl groups optionally substituted; or R.sub.3 and R.sub.4, in general formulae (VIII) or (IX), can be optionally bound to each other so as to form, together with the other atoms to which they are bound, a cycle containing from 1 to 12 carbon atoms, saturated, unsaturated, or aromatic, optionally substituted with linear or branched C.sub.1-C.sub.20 alkyl groups, saturated or unsaturated, optionally containing heteroatoms, aryl groups optionally substituted, heteroaryl groups optionally substituted, cycloalkyl groups optionally substituted, heterocyclic groups optionally substituted, trialkyl- or triaryl-silyl groups, dialkyl- or diaryl-amine groups, dialkyl- or diaryl phosphinic groups, linear or branched C.sub.1-C.sub.20 alkoxyl groups, saturated or unsaturated, aryloxyl groups optionally substituted, thioalkoxyl or thioaryloxyl groups optionally substituted, cyano groups, said cycle optionally containing heteroatoms selected from oxygen, sulfur, nitrogen, silicon, phosphorous, selenium; m, r and s, the same or different, are an integer ranging from 0 to 5, with the proviso that at least one of m, r and s is different from 0, and that at least one of m, r and s is different from 0 for said at least one of P.sub.1, P.sub.2 and P.sub.3 that is selected from bivalent heteroaryl groups having general formula (VIII) or (IX); A represents a group COOH; a phosphonic group having formula PO(OH).sub.2 or PO(OH)(R), wherein R is selected from linear or branched C.sub.1-C.sub.20 alkyl groups; a carboxycyanovinylene group having general formula (XIII) or (XIV): ##STR00083## ##STR00084## ##STR00085## wherein R.sub.8, R.sub.9 and R.sub.10, the same or different, represent a hydrogen atom; or they represent a halogen atom selected from fluorine, chlorine or bromine; or they are selected from linear or branched C.sub.1-C.sub.20 alkyl groups, saturated or unsaturated, optionally containing heteroatoms, aryl groups optionally substituted, heteroaryl groups optionally substituted, cycloalkyl groups optionally substituted, cyano groups, nitro groups; t is an integer ranging from 2 to 6; D represents a triarylamine group having the following general formulae (XV), (XVI), (XVII), (XVIII), (XIX), (XX), (XXI), (XXII), (XXIII), (XXIV): ##STR00086## ##STR00087## ##STR00088## wherein R.sub.11 represents an hydrogen atom or it is selected from linear or branched C.sub.1-C.sub.20 alkyl groups, saturated or unsaturated, optionally containing heteroatoms, linear or branched C.sub.1-C.sub.20 alkoxyl groups, saturated or unsaturated, polyethyleneoxyl groups having formula RO[CH.sub.2CH.sub.2O].sub.q wherein R represents a hydrogen atom; or it is selected from linear or branched C.sub.1-C.sub.20 alkyl groups, and q is an integer ranging from 1 to 20, aryl groups optionally substituted, heteroaryl groups optionally substituted, cycloalkyl groups optionally substituted, heterocyclic groups optionally substituted, trialkyl- or triaryl-silyl groups, dialkyl- or diaryl-amine groups, dialkyl- or diaryl phosphinic groups, linear or branched C.sub.1-C.sub.20 alkoxyl groups, saturated or unsaturated, aryloxyl groups optionally substituted, thioalkoxyl or thioaryloxyl groups optionally substituted.
8. A dye-sensitized photoelectric transformation element, comprising at least one organic dye having general formula (I) according to claim 7, said dye-sensitized photoelectric transformation element being supported on particles of a semiconductor oxide.
9. A Dye-Sensitized Solar Cell (DSSC) comprising the dye-sensitized photoelectric transformation element according to claim 8.
Description
EXAMPLES
(1) Reagents and Materials
(2) The reagents and materials used in the following examples of the invention, their optional pretreatments and their producer, are indicated in the following list: tetrahydrofuran (THF) of Aldrich: anhydrified by distillation on lithium aluminium hydride (LiAlH.sub.4) in an inert atmosphere; potassium t-butoxide (t-BuOK) of Aldrich: used as such; dimethylformamide (DMF) of Aldrich: used as such; phosphorous oxychloride (POCl.sub.3) of Aldrich: used as such; 1,2-dichloroethane of Acros: used as such; 2-cyanoacetic acid of Aldrich: used as such; piperidine of Aldrich: used as such; chloroform (CHCl.sub.3) of Carlo Erba: used as such; dichloromethane (CH.sub.2Cl.sub.2) of Carlo Erba: used as such; ethyl acetate (AcOEt) of Carlo Erba: used as such; sodium sulfate (Na.sub.2SO.sub.4) of Carlo Erba: used as such; potassium carbonate (K.sub.2CO.sub.3) of Aldrich: used as such; 1,1-bis(diphenylphosphine)ferrocene-palladium(II)dichloride [Pd(dppf)Cl.sub.2] complexed with dichloromethane of Aldrich: used as such; methanol (MeOH) of Carlo Erba: used as such; toluene of Carlo Erba: used as such; n-hexane of Carlo Erba: used as such; sodium acetate (AcONa) of Aldrich: used as such; diethyl ether (Et.sub.2O) of Carlo Erba: used as such; N-bromosuccinimide (NBS) of Aldrich: recrystallized from water; ammonium chloride (NH.sub.4Cl) of Carlo Erba: used as such; trimethylsilylacetylene of Aldrich: used as such; bis(triphenylphosphine)palladium(II)dichloride [Pd(PPh.sub.3).sub.2Cl.sub.2] of Aldrich: used as such; triphenylphosphine (PPh.sub.3) of Aldrich: used as such; copper iodide (CuI) of Aldrich: used as such; triethylamine (NEt.sub.3) of Aldrich: used as such; titanium tetrachloride (TiCl.sub.4) of Aldrich: used as such; dimethylsulfoxide (DMSO) of Carlo Erba: used as such. deuterated chloroform (CDCl.sub.3) of Acros: used as such.
(3) The following characterization methods were used in the following examples.
(4) Reactions and Products Obtained
(5) The reactions were carried out by means of thin layer chromatography, on Polygram Sil G/UV254 silica gel having a thickness of 0.20 mm, revealing the spots separated by irradiation of the supports with UV light (254 nm and 365 nm).
(6) The compounds obtained were purified by means of flash chromatography using Merck 9385 silica gel having a particle size ranging from 230 mesh to 400 mesh (40 mm-63 mm) and a pore size equal to 60 . Said flash chromatography was carried out as described by Still, W. C. et al. in Journal of Organic Chemistry (1978), Vol. 43, pages 2923-2925.
(7) NMR Spectra
(8) The NMR spectra of the compounds obtained were carried out using a NMR Bruker ANX-500 spectrometer.
(9) For this purpose, about 10 mg of the sample to be examined were dissolved in about 0.8 ml of a suitable solvent deuterated directly in the glass tube used for the measurement. The scale of the chemical shifts was calibrated in relation to the tetramethylsilane signal set at 0 ppm.
(10) Absorption Spectra
(11) The absorption spectra in a solution of the compounds prepared, in ultraviolet and visible (UV-Vis) (375 nm-800 nm), were acquired in transmission using a Jasco V-570 spectrophotometer.
(12) For this purpose, about 5 mg of the sample to be examined were dissolved in about 10 ml of a suitable solvent: 2 ml of said solution were placed in a quartz cuvette with an optical path of 1 cm.
Example 1
Preparation of the Compound F1
(13) ##STR00049##
(14) The compound F1 was obtained according to the following Scheme 1:
(15) ##STR00050##
wherein: (i) indicates diethyl-thiophen-2-yl-methylphosphonate, potassium t-butoxide (t-BuOK), anhydrous tetrahydrofuran (THF); (ii) indicates dimethylformamide (DMF), phosphorous oxychloride (POCl.sub.3), 1,2-dichloroethane; (iii) indicates 2-cyanoacetic acid, piperidine, chloroform (CHCl.sub.3).
Synthesis of N,N-bis-{4-[(thien-2-yl)vin-2-yl]phenyl}-p-methoxyaniline (2)
(16) 0.63 g (1.9 mmoles) of N,N-bis-(4-formylphenyl)aniline (1) [obtained as described by El-Khouly M. E. et al., in The Journal of Physical Chemistry B (2008), Vol. 112, pages 3910-3917], 1.17 g (5.0 mmoles) of diethyl thiophen-2-yl-methylphosphonate [obtained as described by Wang Z.-S. et al., in The Journal of Physical Chemistry C (2007), Vol. 111, pages 7224-7230] and 30 ml of anhydrous tetrahydrofuran (THF), were introduced into a 250 ml flask: 0.56 g (5.0 mmoles) of potassium t-butoxide (t-BuOK) were then added, in small portions, to the solution obtained. The reaction mixture obtained was left, under stirring, at room temperature (25 C.), for 16 hours. The reaction was then quenched by adding 30 ml of water and subsequently 30 ml of ethyl acetate (AcOEt) and the whole mixture was left, under stirring, for 1 hour and then extracted with dichloromethane (CH.sub.2Cl.sub.2) (320 ml). The organic phase obtained was washed with water (315 ml) and dried on sodium sulfate (Na.sub.2SO.sub.4). After eliminating the solvent by evaporation at reduced pressure, a brown-coloured residue was obtained, which was purified by means of flash chromatography on silica gel, using dichloromethane (CH.sub.2Cl.sub.2) as eluent, obtaining 0.43 g (yield 46%) of N,N-bis-{4-[(thien-2-yl)vin-2-yl]phenyl}-p-methoxyaniline (2), as an orange solid, having a melting point of 173 C.-174 C.
(17) Said N,N-bis-{4-[(thien-2-yl)vin-2-yl]phenyl}-p-methoxyaniline (2) was characterized by means of .sup.1H-NMR (500 MHz; CDCl.sub.3; Me.sub.4Si) obtaining the following spectrum: .sub.H 7.32 (4 H, d, J 8.6), 7.16 (2 H, t, J 5.0), 7.11 (2 H, d, J 15.9), 7.09 (2 H, d, J 8.9), 7.04-6.97 (8 H, m), 6.89-6.84 (4 H, m), 3.80 (3 H, s).
Synthesis of N,N-bis-{4-[(5-formylthien-2-yl)vin-2-yl]phenyl}-p-methoxyaniline (3)
(18) 0.32 g (4.4 mmoles) of dimethyl formamide (DMF) were introduced into a 100 ml flask, previously anhydrified and maintained under a flow of nitrogen (N.sub.2), and subsequently, after cooling to a temperature of 10 C., 0.68 g (4.4 mmoles) of phosphorous oxychloride (POCl.sub.3) were slowly added dropwise: the formation of a vitreous white solid was observed and after 30 minutes, 20 ml of 1,2-dichloroethane were added. After the complete dissolution of the reaction mixture, 0.43 g (0.87 mmoles) of N,N-bis-{4-[(thien-2-yl)vin-2-yl]phenyl}-p-methoxyaniline (2), obtained as described above, dissolved in 30 ml of 1,2-dichloroethane, were added. The reaction mixture was left, under stirring, at room temperature (25 C.), for 16 hours. The reaction was then quenched by adding 50 ml of a saturated aqueous solution of potassium carbonate (K.sub.2CO.sub.3) and the whole mixture was left, under stirring, for 1 hour, and then extracted with dichloromethane (CH.sub.2Cl.sub.2) (320 ml). The organic phase obtained was washed with water (215 ml) and dried on sodium sulfate (Na.sub.2SO.sub.4). After eliminating the solvent by evaporation at reduced pressure, 0.44 g (yield 92%) of N,N-bis-{4-[(5-formylthien-2-yl)vin-2-yl]phenyl}-p-methoxyaniline (3) were obtained, as a dark orange solid.
(19) Said N,N-bis-{4-[(5-formylthien-2-yl)vin-2-yl]-phenyl}-p-methoxyaniline (3) was characterized by means of .sup.1H-NMR (500 MHz; CDCl.sub.3; Me.sub.4Si) obtaining the following spectrum: .sub.H 9.85 (1 H, s), 7.65 (2 H, d, J 3.9), 7.37 (4 H, d, J 8.7), 7.13-7.08 (8 H, m), 7.04 (4 H, d, J 8.7), 6.88 (2 H, d, J 8.9), 3.80 (3 H, s).
Synthesis of the Compound (F1)
(20) 0.44 g (0.80 mmoles) of N,N-bis-{4-[(5-formylthien-2-yl)vin-2-yl]phenyl}-p-methoxyaniline (3), obtained as described above, and 30 ml of chloroform (CHCl.sub.3), were introduced into a 50 ml flask: 0.41 g (4.8 mmoles) of 2-cyanoacetic acid were then added to the solution obtained. The reaction mixture obtained was cooled to 0 C. with an ice bath and a solution of piperidine (0.54 g, 6.4 mmoles) in 5 ml of chloroform (CHCl.sub.3) was subsequently slowly added dropwise. At the end of the dripping, the reaction mixture was heated to the reflux temperature of the solvent, for 8 hours. The reaction mixture was then left to cool to room temperature (25 C.) and the formation of a precipitate was observed, which was recovered by filtration at reduced pressure obtaining a dark red solid which was subsequently dissolved in 20 ml of water and treated with 10 ml of a solution of hydrochloric acid at 10%: in this phase, the formation of a dark precipitate was observed, which was in its turn recovered by filtration at reduced pressure, washed with water (215 ml) and dried under vacuum obtaining 0.25 g (yield 56%) of the compound (F1) as a purple solid.
(21) Said compound (F1) was characterized by means of .sup.1H-NMR (500 MHz; DMSO-d.sub.6; Me.sub.4Si) obtaining the following spectrum: .sub.H 8.45 (2H, s), 7.94 (2 H, d, J 4.0), 7.59 (4 H, d, J 8.7), 7.45 (2 H, d, J 16.1), 7.41 (2 H, d, J 4.0), 7.23 (2 H, d, J 16.1), 7.12 (2 H, d, J 8.9), 7.00 (2 H, d, J 9.1), 6.98 (4 H, d, J 8.7), 3.78 (3H, s).
Example 2
Preparation of the Compound F2
(22) ##STR00051##
(23) The compound F2 was obtained according to the following Scheme 2:
(24) ##STR00052##
wherein: (i) indicates 5-(4,4,4,5,5-tetramethyl-1,3,2-dioxaborolan)thieno[3,2-b]thiophene, 1,1-bis(diphenyl-phosphine)ferrocene-palladium(II)dichloride complexed with dichloromethane [Pd(dppf)Cl.sub.2], potassium carbonate (K.sub.2CO.sub.3), methanol (MeOH), toluene; (ii) indicates dimethylformamide (DMF), phosphorous oxychloride (POCl.sub.3), 1,2-dichloroethane; (iii) indicates 2-cyanoacetic acid, piperidine, chloroform (CHCl.sub.3).
Synthesis of 4-methoxy-N,N-bis-(4-(thieno[3,2-b]thien-5-yl)phenyl)aniline (5)
(25) 6 ml of a mixture of methanol (MeOH)/toluene 1:1 v/v, 0.33 g (0.75 mmoles) of 4-methoxy-N,N-bis-(4-bromophenyl)aniline (4) [obtained as described by Chang H.-W. et al, in Journal of Polymer Science Part A: Polymer Chemistry (2009), Vol. 47, pages 4037-4050], 0.60 g (2.3 mmoles) of 5-(4,4,4,5,5-tetramethyl-1,3,2-dioxaborolan)-thieno[3,2-b]thiophene [obtained as described by Alesi S. et al., in Green Chemistry (2008) Vol. 10, pages 517-523], 0.12 g (0.15 mmoles) of 1,1-bis(diphenylphosphine)ferrocene-palladium(II)dichloride complexed with dichloromethane [Pd(dppf)Cl.sub.2] and 1.06 g (8.3 mmoles) of potassium carbonate (K.sub.2CO.sub.3), were introduced into a 50 ml microwave test-tube. The test-tube was then sealed and heated with microwaves to 70 C., 50 W, for 20 minutes. 20 ml of dichloromethane (CH.sub.2Cl.sub.2) were then added and the whole mixture was poured into 50 ml of a saturated aqueous solution of ammonium chloride (NH.sub.4Cl) and extracted with dichloromethane (CH.sub.2Cl.sub.2) (320 ml). The organic phase obtained was washed with water (215 ml) and dried on sodium sulfate (Na.sub.2SO.sub.4). After eliminating the solvent by evaporation at reduced pressure, a crude oil was obtained, which was purified by means of flash chromatography on silica gel, using as eluent a mixture of n-hexane/dichloromethane (CH.sub.2Cl.sub.2) (1:1, v/v), obtaining 0.36 g (yield 87%) of 4-methoxy-N,N-bis-(4-(thieno[3,2-b]thien-5-yl)phenyl)aniline (5), as a yellow solid, having a melting point of 140 C.-141 C.
(26) Said 4-methoxy-N,N-bis-(4-(thieno[3,2-b]thien-5-yl)phenyl)aniline (5) was characterized by means of .sup.1H-NMR (500 MHz; CDCl.sub.3; Me.sub.4Si) obtaining the following spectrum: .sub.H 7.77 (2 H, s), 7.65 (2 H, d, J 5.3), 7.61 (4 H, d, J 8.7), 7.44 (2 H, d, J 5.1), 7.13 (2 H, d, J 8.9), 7.04 (4 H, d, J 8.7), 6.99 (2 H, d, J 8.9), 3.80 (3 H, s).
Synthesis of 4-methoxy-N,N-bis-(4-(5-formyl-thieno-[3,2-b]thien-5-yl)phenyl)aniline (6)
(27) 0.11 g (1.4 mmoles) of dimethyl formamide (DMF) were introduced into a 50 ml flask, previously anhydrified and maintained under a flow of nitrogen (N.sub.2), and subsequently, after cooling to a temperature of 10 C., 0.22 g (1.4 mmoles) of phosphorous oxychloride (POCl.sub.3) were slowly added dropwise: the formation of a vitreous white solid was observed and after 30 minutes, 10 ml of 1,2-dichloroethane were added. After the complete dissolution of the reaction mixture, 0.36 g (0.65 mmoles) of 4-methoxy-N,N-bis-(4-(thieno[3,2-b]thien-5-yl)phenyl)aniline (5), obtained as described above, dissolved in 15 ml of 1,2-dichloroethane, were added. The reaction mixture was left, under stirring, at 70 C., for 4 hours. The reaction was then quenched by adding 20 ml of a saturated aqueous solution of sodium acetate (AcONa) and the whole mixture was left, under stirring, for 1 hour, and then extracted with dichloromethane (CH.sub.2Cl.sub.2) (315 ml). The organic phase obtained was washed with water (215 ml) and dried on sodium sulfate (Na.sub.2SO.sub.4). After eliminating the solvent by evaporation at reduced pressure, 0.13 g (yield 34%) of 4-methoxy-N,N-bis-(4-(5-formyl-thieno-[3,2-b]thien-5-yl)phenyl)aniline (6) were obtained, as a dark orange solid, having a melting point of 225 C.-226 C.
(28) Said 4-methoxy-N,N-bis-(4-(5-formyl-thieno-[3,2-b]thien-5-yl)phenyl)aniline (6) was characterized by means of .sup.1H-NMR (500 MHz; CDCl.sub.3; Me.sub.4Si) obtaining the following spectrum: .sub.H 9.96 (2 H, s), 8.40 (2 H, s), 7.92 (2 H, s), 7.70 (4 H, d, J 8.5), 7.15 (2 H, d, J 8.6), 7.10 (4 H, d, J 8.5), 7.02 (2 H, d, J 8.6), 3.80 (3 H, s).
Synthesis of the Compound F2
(29) 0.13 g (0.22 mmoles) of 4-methoxy-N,N-bis-(4-(thieno[3,2-b]thien-5-yl)phenyl)aniline (5), obtained as described above, and 10 ml of chloroform (CHCl.sub.3) were introduced into a 50 ml flask: 0.19 g (2.2 mmoles) of 2-cyanoacetic acid were then added to the solution obtained. The reaction mixture obtained was cooled to 0 C. with an ice bath and a solution of piperidine (0.21 g, 2.5 mmoles) in 5 ml of chloroform (CHCl.sub.3) was subsequently slowly added dropwise. At the end of the dripping, the reaction mixture was heated to the reflux temperature of the solvent, for 8 hours. The reaction mixture was then left to cool to room temperature (25 C.) and the solvent was eliminated by evaporation at reduced pressure, obtaining a dark orange crude oil. The crude oil obtained was subsequently dissolved in 10 ml of water and treated with 5 ml of an aqueous solution of hydrochloric acid at 10%: in this phase, the formation of a dark precipitate was observed, which was recovered by filtration at reduced pressure, washed with water (215 ml) and dried under vacuum obtaining 0.07 g (yield 41%) of the compound (F2) as a purple solid having a melting point >250 C.
(30) Said compound (F2) was characterized by means of .sup.1H-NMR (500 MHz; DMSO-d.sub.6; Me.sub.4Si) obtaining the following spectrum: .sub.H 8.56 (2H, s), 8.31 (2H, s), 7.95 (2 H, 5), 7.69 (4 H, d, J 8.6), 7.16 (2 H, d, J 8.8), 7.09 (4 H, d, J 8.7), 7.01 (2 H, d, J 8.8), 3.80 (3H, s).
Example 3
Preparation of the Compound (F3)
(31) ##STR00053##
(32) The compound (F3) was obtained according to the following Scheme 3:
(33) ##STR00054##
wherein: (i) indicates 5-(4,4,4,5,5-tetramethyl-1,3,2-dioxaborolan)thieno[3,2-b]thiophene, 1,1-bis(diphenyl-phosphine)ferrocene-palladium(II)dichloride complexed with dichloromethane [Pd(dppf)Cl.sub.2], potassium carbonate (K.sub.2CO.sub.3), methanol (MeOH), toluene; (ii) indicates dimethylformamide (DMF), phosphorous oxychloride (POCl.sub.3); (iii) indicates 2-cyanoacetic acid, piperidine, chloroform (CHCl.sub.3).
Synthesis of 4-octyloxy-N,N-bis-(4-(thieno[3,2-b]thien-5-yl)phenyl)aniline (8)
(34) 12 ml of a mixture of methanol (MeOH)/toluene 1:1 v/v, 0.70 g (1.3 mmoles) of 4-octyloxy-N,N-bis-(4-bromophenyl)aniline (7) [obtained as described by Blankenburg L. et al., Journal of Applied Polymer Science (2009), Vol. 111, pages 1850-1861], 1.05 g (3.9 mmoles) of 5-(4,4,4,5,5-tetramethyl-1,3,2-dioxaborolan)thieno[3,2-b]thiophene [obtained as described by Alesi S. et al., in Green Chemistry (2008) Vol. 10, pages 517-523], 0.22 g (0.27 mmoles) of 1,1-bis(diphenylphosphine)ferrocene-palladium(II)dichloride complexed with dichloromethane [Pd(dppf)Cl.sub.2] and 1.86 g (14.5 mmoles) of potassium carbonate (K.sub.2CO.sub.3), were introduced into a 50 ml microwave test-tube. The test-tube was then sealed and heated with microwaves to 70 C., 50 W, for 10 minutes. 20 ml of dichloromethane (CH.sub.2Cl.sub.2) were then added and the whole mixture was poured into 50 ml of a saturated aqueous solution of ammonium chloride (NH.sub.4Cl) and extracted with dichloromethane (CH.sub.2Cl.sub.2) (320 ml). The organic phase obtained was washed with water (215 ml) and dried on sodium sulfate (Na.sub.2SO.sub.4). After eliminating the solvent by evaporation at reduced pressure, a crude oil was obtained, which was purified by means of flash chromatography on silica gel, using as eluent a mixture of n-hexane/diethyl ether (Et.sub.2O) (8:2, v/v), obtaining 0.71 g (yield 92%) of 4-octyloxy-N,N-bis-(4-(thieno[3,2-b]thien-5-yl)phenyl)aniline (8), as a yellow solid.
(35) Said 4-octyloxy-N,N-bis-(4-(thieno[3,2-b]thien-5-yl)phenyl)aniline (8) was characterized by means of .sup.1H-NMR (500 MHz; CDCl.sub.3; Me.sub.4Si) obtaining the following spectrum: .sub.H 7.77 (2 H, s), 7.65 (2 H, d, J 5.3), 7.61 (4 H, d, J 8.7), 7.44 (2 H, d, J 5.1), 7.13 (2 H, d, J 8.9), 7.04 (4 H, d, J 8.7), 6.99 (2 H, d, J 8.9), 3.98 (2 H, t, J 6.4), 1.73 (2 H, quintet, J 7.0), 1.66 (2 H, quintet, J 7.1), 1.37-1.22 (8 H, m), 0.88 (3 H, t, J 6.7).
Synthesis of 4-octyloxy-N,N-bis-(4-(5-formyl-thieno-[3,2-b]thien-5-yl)phenyl)aniline (9)
(36) 0.28 g (3.9 mmoles) of dimethyl formamide (DMF) were introduced into a 100 ml flask, previously anhydrified and maintained under a flow of nitrogen (N.sub.2), and subsequently, after cooling to a temperature of 10 C., 0.59 g (3.9 mmoles) of phosphorous oxychloride (POCl.sub.3) were slowly added dropwise: the formation of a vitreous white solid was observed and after 30 minutes, 10 ml of dimethylformamide (DMF) were added. After the complete dissolution of the reaction mixture, 0.71 g (1.3 mmoles) of 4-octyloxy-N,N-bis-(4-(thieno[3,2-b]thien-5-yl)phenyl)aniline (8), obtained as described above, dissolved in 25 ml of dimethylformamide, were added. The reaction mixture was left, under stirring, at 70 C., for 4 hours. The reaction was then quenched by adding 40 ml of a saturated aqueous solution of sodium acetate (AcONa) and the whole mixture was left, under stirring, for 1 hour and then extracted with dichloromethane (CH.sub.2Cl.sub.2) (315 ml). The organic phase obtained was washed with water (215 ml) and dried on sodium sulfate (Na.sub.2SO.sub.4). After eliminating the solvent by evaporation at reduced pressure, a crude oil was obtained, which was purified by means of flash chromatography on silica gel using as eluent, a mixture of n-hexane/diethyl ether (Et.sub.2O) (8:2, v/v), obtaining 0.20 g (yield 22%) of 4-octyloxy-N,N-bis-(4-(5-formyl-thieno-[3,2-b]thien-5-yl)phenyl)-aniline (9), as a dark orange oil.
(37) Said 4-octyloxy-N,N-bis-(4-(5-formyl-thieno-[3,2-b]thien-5-yl)phenyl)aniline (9) was characterized by means of .sup.1H-NMR (500 MHz; CDCl.sub.3; Me.sub.4Si) obtaining the following spectrum: .sub.H 9.87 (2 H, s), 8.39 (2 H, s), 7.92 (2 H, s), 7.69 (4 H, d, J 8.6), 7.14 (2 H, d, J 8.8), 7.08 (4 H, d, J 8.6), 7.00 (2 H, d, J 8.8), 3.98 (2 H, t, J 6.4), 1.73 (2 H, quintet, J 7.0), 1.66 (2 H, quintet, J 7.1), 1.37-1.22 (8 H, m), 0.88 (3 H, t, J 6.7).
Synthesis of the Compound F3
(38) 0.20 g (0.28 mmoles) of 4-octyloxy-N,N-bis-(4-(5-formyl-thieno-[3,2-b]thien-5-yl)phenyl)aniline (9), obtained as described above, and 10 ml of chloroform (CHCl.sub.3), were introduced into a 50 ml flask: 0.24 g (2.8 mmoles) of 2-cyanoacetic acid were then added to the solution obtained. The reaction mixture obtained was cooled to 0 C. with an ice bath and a solution of piperidine (0.25 g, 3.0 mmoles) in 5 ml of chloroform (CHCl.sub.3) was subsequently slowly added dropwise. At the end of the dripping, the reaction mixture was heated to the reflux temperature of the solvent, for 16 hours. The reaction mixture was then left to cool to room temperature (25 C.) and the solvent was eliminated by evaporation at reduced pressure, obtaining a dark orange crude oil. The crude oil obtained was subsequently dissolved in 10 ml of water and treated with 5 ml of an aqueous solution of hydrochloric acid at 10%: in this phase, the formation of a dark precipitate was observed, which was recovered by filtration at reduced pressure, washed with water (215 ml) and dried under vacuum obtaining 0.17 g (yield 71%) of the compound (F3) as a purple solid having a melting point >250 C.
(39) Said compound (F3) was characterized by means of .sup.1H-NMR (500 MHz; DMSO-d.sub.6; Me.sub.4Si) obtaining the following spectrum: .sub.H 8.57 (2H, s), 8.32 (2H, s), 7.95 (2 H, s), 7.69 (4 H, d, J 8.7), 7.14 (2 H, d, J 8.8), 7.08 (4 H, d, J 8.7), 6.99 (2 H, d, J 8.9), 3.98 (2 H, t, J 6.4), 1.73 (2 H, quintet, J 7.0), 1.66 (2 H, quintet, J 7.1), 1.37-1.22 (8 H, m), 0.88 (3 H, t, J 6.7).
Example 4
Preparation of the Compound (F4)
(40) ##STR00055##
(41) The compound (F4) was obtained according to the following Scheme 4:
(42) ##STR00056## ##STR00057##
wherein: (i) indicates N-bromosuccinimide (NBS), dimethylformamide (DMF); (ii) indicates 5-(4,4,4,5,5-tetramethyl-1,3,2-dioxaborolan)thieno[3,2-b]thiophene, 1,1-bis(diphenyl-phosphine)ferrocene-palladium(II)-dichloride complexed with dichloromethane [Pd(dppf)Cl.sub.2], potassium carbonate (K.sub.2CO.sub.3), methanol (MeOH), toluene; (iii) indicates dimethylformamide (DMF), phosphorous oxychloride (POCl.sub.3); (iv) indicates 2-cyanoacetic acid, piperidine, chloroform (CHCl.sub.3).
Synthesis of 4-(1-{2-[2-(2-methoxyethoxy)ethoxy]-ethoxy})-N,N-bis-(4-bromophenyl)aniline (11)
(43) 0.38 g (0.93 mmoles) of 4-(1-{2-[2-(2-methoxy-ethoxy)ethoxy]})-N,N-bis-(phenyl)aniline (10), [obtained as described by Willinger K. et al., in Journal of Materials Chemistry (2009), Vol. 19, pages 5364-5376], and 10 ml of dimethylformamide (DMF), were introduced into a 50 ml flask, and a solution of N-bromosuccinimide (NBS) (0.33 g, 1.9 mmoles) in 5 ml of dimethylformamide (DMF) was then slowly added dropwise, after cooling the solution to 0 C. with an ice bath. At the end of the dripping, the reaction mixture was heated to room temperature (25 C.) and kept, under stirring, for 16 hours. The reaction mixture was then poured into a 250 ml flask containing 75 ml of water and 20 ml of diethyl ether (Et.sub.2O) and was extracted with diethyl ether (Et.sub.2O) (315 ml). The organic phase obtained was dried on sodium sulfate (Na.sub.2SO.sub.4) and the solvent was eliminated by evaporation at reduced pressure, obtaining 0.37 g (yield 71%) of 4-(1-{2-[2-(2-methoxyethoxy)ethoxy]ethoxy})-N,N-bis-(4-bromophenyl)aniline (11) as a brown oil.
(44) Said 4-(1-{2-[2-(2-methoxyethoxy)ethoxy]ethoxy})-N,N-bis-(4-bromophenyl)aniline (11) was characterized by means of .sup.1H-NMR (500 MHz; CDCl.sub.3; Me.sub.4Si) obtaining the following spectrum: .sub.H 7.29 (4 H, d, J 8.8), 7.00 (2 H, d, J 8.9), 6.87 (4 H, d, J 8.8), 6.85 (2 H, d, J 8.9), 4.11 (2 H, t, J 5.1), 3.85 (2 H, t, J 4.7), 3.78-3.74 (2 H, m), 3.72-3.66 (4 H, m), 3.58-3.54 (2 H, s), 3.37 (3 H, s)
Synthesis of 4-(1-{2-[2-(2-methoxyethoxy)ethoxy]-ethoxy})-N,N-bis-(4-(thieno[3,2-b]thien-5-yl)phenyl)-aniline (12)
(45) 12 ml of a mixture of methanol (MeOH)/toluene (1:1 v/v), 0.37 g (0.66 mmoles) of 4-(1-{2-[2-(2-methoxyethoxy)ethoxy]ethoxy})-N,N-bis-(4-bromophenyl)-aniline (11) [obtained as described above], 0.53 g (0.66 mmoles) of 5-(4,4,4,5,5-tetramethyl-1,3,2-dioxaborolan)-thieno[3,2-b]thiophene [obtained as described by Alesi S. et al., in Green Chemistry (2008), Vol. 10, pages 517-523], 0.05 g (0.06 mmoles) of 1,1-bis(diphenylphosphine)ferrocene-palladium(II)dichloride complexed with dichloromethane [Pd(dppf)Cl.sub.2] and 1.0 g (7.3 mmoles) of potassium carbonate (K.sub.2CO.sub.3), were introduced into a 50 ml microwave test-tube. The test-tube was then sealed and heated with microwaves to 70 C., 50 W, for 20 minutes. 20 ml of ethyl acetate (AcOEt) were then added and the whole mixture was poured into a 100 ml flask containing 40 ml of a saturated aqueous solution of ammonium chloride (NH.sub.4Cl) and subsequently extracted with ethyl acetate (AcOEt) (320 ml). The organic phase obtained was dried on sodium sulfate (Na.sub.2SO.sub.4) and the solvent was eliminated by evaporation at reduced pressure. A crude oil was obtained, which was purified by means of flash chromatography on silica gel, using as eluent a mixture of diethyl ether (Et.sub.2O)/ethyl acetate (AcOEt) (8:2, v/v), obtaining 0.32 g (yield 71%) of 4-(1-{2-[2-(2-methoxyethoxy)ethoxy]ethoxy})-N,N-bis-(4-(thieno[3,2-b]thien-5-yl)phenyl)aniline (12), as a yellow solid.
(46) Said 4-(1-{2-[2-(2-methoxyethoxy)ethoxy]ethoxy})-N,N-bis-(4-(thieno[3,2-b]thien-5-yl)phenyl)aniline (12) was characterized by means of .sup.1H-NMR (500 MHz; CDCl.sub.3; Me.sub.4Si) obtaining the following spectrum: .sub.H 7.48 (4 H, d, J 8.7), 7.39 (2 H, s), 7.32 (2 H, d, J 5.2), 7.23 (2 H, d, J 5.2), 7.12 (2 H, d, J 8.9), 7.08 (4 H, d, J 8.7), 6.90 (2 H, d, J 8.9), 4.14 (2 H, t, J 4.7), 3.87 (2 H, t, J 4.7), 3.78-3.74 (2 H, m), 3.70-3.63 (4 H, m), 3.58-3.54 (2 H, s), 3.39 (3 H, s).
Synthesis of 4-(1-{2-[2-(2-methoxyethoxy)ethoxy]-ethoxy})-N,N-bis-(4-(5-formyl-thieno[3,2-b]thien-5-yl)phenyl)aniline (13)
(47) 0.08 g (1.1 mmoles) of dimethyl formamide (DMF) were introduced into a 100 ml flask, previously anhydrified and maintained under a flow of nitrogen (N.sub.2), and subsequently, after cooling to a temperature of 10 C., 0.17 g (1.1 mmoles) of phosphorous oxychloride (POCl.sub.3) were slowly added dropwise: the formation of a vitreous white solid was observed and after 30 minutes, 5 ml of dimethylformamide (DMF) were added. After the complete dissolution of the reaction mixture, 0.32 g (0.47 mmoles) of 4-(1-{2-[2-(2-methoxyethoxy)ethoxy]ethoxy})-N,N-bis-(4-(thieno[3,2-b]thien-5-yl)phenyl)aniline (12), obtained as described above, dissolved in 20 ml of dimethylformamide, were added. The reaction mixture was left, under stirring, at 70 C., for 4 hours. The reaction was then quenched in a saturated aqueous solution of sodium acetate (AcONa) and the whole mixture was left, under stirring, for 1 hour and then extracted with dichloromethane (CH.sub.2Cl.sub.2) (330 ml). The organic phase obtained was washed with water (220 ml) and dried on sodium sulfate (Na.sub.2SO.sub.4). After eliminating the solvent by evaporation at reduced pressure, a crude oil was obtained, which was purified by means of flash chromatography on silica gel using as eluent, a mixture of diethyl ether (Et.sub.2O)/dichloromethane (CH.sub.2Cl.sub.2) (2:1 v/v), obtaining 0.17 g (yield 49%) of 4-(1-{2-[2-(2-methoxyethoxy)ethoxy]-ethoxy})-N,N-bis-(4-(5-formyl-thieno[3,2-b]thien-5-yl)phenyl)aniline (13), as a dark orange solid.
(48) Said 4-(1-{2-[2-(2-methoxyethoxy)ethoxy]ethoxy})-N,N-bis-(4-(5-formyl-thieno[3,2-b]thien-5-yl)phenyl)-aniline (13) was characterized by means of .sup.1H-NMR (500 MHz; DMSO-d.sub.6; Me.sub.4Si) obtaining the following spectrum: .sub.H 9.96 (2 H, s), 8.38 (2 H, s), 7.90 (2 H, s), 7.67 (2 H, d, J 8.7), 7.13 (4 H, d, J 8.9), 7.07 (2 H, d, J 8.7), 7.02 (4 H, d, J 8.9), 4.12 (2 H, t, J 4.7), 3.76 (2 H, t, J 4.5), 3.62-3.58 (2 H, m), 3.57-3.50 (4 H, m), 3.46-3.42 (2 H, s), 3.25 (3 H, s).
Synthesis of the compound (F4)
(49) 0.17 g (0.23 mmoles) of 4-(1-{2-[2-(2-methoxyethoxy)ethoxy]ethoxy})-N,N-bis-(4-(5-formyl-thieno[3,2-b]thien-5-yl)phenyl)aniline (13), obtained as described above, and 10 ml of chloroform (CHCl.sub.3) were introduced into a 50 ml flask: 0.19 g (2.3 mmoles) of 2-cyanoacetic acid were then added to the solution obtained. The reaction mixture was cooled to 0 C. with an ice bath and a solution of piperidine (0.22 g, 2.6 mmoles) in 5 ml of chloroform (CHCl.sub.3) was subsequently slowly added dropwise. At the end of the dripping, the reaction mixture was heated to the reflux temperature of the solvent, for 10 hours. The reaction mixture was then left to cool to room temperature (25 C.) and the solvent was eliminated by evaporation at reduced pressure, obtaining a dark orange crude oil which was dissolved in 50 ml of water and treated with 20 ml of an aqueous solution of hydrochloric acid at 10%: in this phase, the formation of a dark precipitate was observed, which was recovered by filtration at reduced pressure, washed with water (215 ml) and dried under vacuum obtaining 0.12 g (yield 61%) of the compound (F4) as a purple solid, having a melting point >250 C.
(50) Said compound (F4) was characterized by means of .sup.1H-NMR (500 MHz; DMSO-d.sub.6; Me.sub.4Si) obtaining the following spectrum: .sub.H 8.50 (2 H, s), 8.27 (2 H, s), 7.93 (2 H, s), 7.67 (4 H, d, J 8.7), 7.14 (2 H, d, J 9.0), 7.08 (4 H, d, J 8.7), 7.02 (2 H, d, J 9.0), 4.12 (2 H, t, J 4.7), 3.76 (2 H, t, J 4.5), 3.62-3.58 (2 H, m), 3.56-3.50 (4 H, m), 3.46-3.42 (2 H, s), 3.25 (3 H, s).
(51) Said compound (F4) was also characterized by means of .sup.13C-NMR (125,77 MHz; DMSO-d.sub.6; Me.sub.4Si) obtaining the following spectrum: .sub.C 164.16, 156.67, 152.22, 148.09, 147.50, 147.09, 139.04, 137.81, 137.23, 132.26, 128.58, 127.56, 123.01, 117.43, 116.43, 116.24, 71.78, 70.44, 70.31, 70.11, 69.43, 67.91, 58.55.
Example 5
Preparation of the Compound (F5)
(52) ##STR00058##
(53) The compound (F5) was prepared according to the following Scheme 5:
(54) ##STR00059##
wherein: (i) indicates N-bromosuccinimide (NBS), dimethylformamide (DMF); (ii) indicates 5-(4,4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-2,3-dihydro-thieno[3,4-b][1,4]dioxin, 1,1-bis(diphenylphosphine)-ferrocene-palladium(II)-dichloride complexed with dichloromethane [Pd(dppf)Cl.sub.2], potassium carbonate (K.sub.2CO.sub.3), methanol (MeOH), toluene; (iii) indicates N-bromosuccinimide (NBS), dimethylformamide (DMF), 5-(4,4,4,5,5-tetramethyl-1,3,2-dioxaborolan)thieno[3,2-b]thiophene, 1,1-bis(diphenylphosphine)ferrocene-palladium(II)dichloride complexed with dichloromethane [Pd(dppf)Cl.sub.2], potassium carbonate (K.sub.2CO.sub.3), methanol (MeOH), toluene; (iv) indicates dimethylformamide (DMF), phosphorous oxychloride (POCl.sub.3); (v) indicates 2-cyanoacetic acid, piperidine, chloroform (CHCl.sub.3).
Synthesis of 4-hexyloxy-N,N-bis-(4-bromophenyl)aniline (15)
(55) 0.83 g (2.4 mmoles) of 4-hexyloxy-N,N-bis-(phenyl)aniline (14), [obtained as described by Li Z. A. et al., in Journal of Polymer Science Part A: Polymer Chemistry (2011), Vol. 49, pages 1977-1987], and 10 ml of dimethylformamide (DMF) (10 ml), were introduced into a 50 ml flask. The solution obtained was cooled to 0 C. with an ice bath and a solution of N-bromosuccinimide (NBS) (0.434 g, 2.4 mmoles) in 5 ml of dimethylformamide (DMF) was then slowly added dropwise. At the end of the dripping, the reaction mixture was heated to room temperature (25 C.) and left, under stirring, for 16 hours. The reaction mixture was then poured into a 250 ml flask containing 75 ml of water and 20 ml of diethyl ether (Et.sub.2O) and extracted with diethyl ether (Et.sub.2O) (315 ml). The organic phase obtained was dried on sodium sulfate (Na.sub.2SO.sub.4) and the solvent was eliminated by evaporation at reduced pressure, obtaining 1.10 g (yield 92%) of 4-hexyloxy-N,N-bis-(4-bromophenyl)aniline (15), as a colourless oil.
(56) Said 4-hexyloxy-N,N-bis-(4-bromophenyl)aniline (15) was characterized by means of .sup.1H-NMR (500 MHz; CDCl.sub.3; Me.sub.4Si) obtaining the following spectrum: .sub.H 7.30 (4 H, d, J 8.8), 7.01 (2 H, d, J 8.9), 6.89 (4 H, d, J 8.9), 6.84 (2 H, d, J 8.9), 3.94 (2 H, t, J 6.5), 1.82-1.74 (2 H, m), 1.50-1.42 (2 H, m), 1.38-1.32 (4 H, m), 0.91 (3 H, t, J 7.1).
Synthesis of 4-hexyloxy-N,N-bis-(4-(3,4-ethylenedioxy-thien-5-yl)aniline (16)
(57) 30 ml of a mixture of methanol (MeOH)/toluene (1:1 v/v), 1.10 g (2.2 mmoles) of 4-hexyloxy-N,N-bis-(4-bromophenyl)aniline (15) [obtained as described above], 2.30 g (8.7 mmoles) of 5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-2,3-dihydrothieno-[3,4-b][1,4]dioxin [obtained as described by A. Zulauf A. et al., in European Journal of Organic Chemistry (2008), Vol. 2008, pages 2118-2129], 0.13 g (0.11 mmoles) of 1,1-bis(diphenylphosphine)ferrocene-palladium(II)dichloride complexed with dichloromethane [Pd(dppf)Cl.sub.2] and 2.70 g (22 mmoles) of potassium carbonate (K.sub.2CO.sub.3), were introduced into a 100 ml microwave test-tube, previously anhydrified and maintained under a flow of nitrogen (N.sub.2). The test-tube was then sealed and heated with microwaves to 70 C., 50 W, for 20 minutes. 50 ml of ethyl acetate (AcOEt) were then added and the whole mixture was poured into a 250 ml flask containing 100 ml of a saturated aqueous solution of ammonium chloride (NH.sub.4Cl) and subsequently extracted with ethyl acetate (AcOEt) (330 ml). The organic phase obtained was dried on sodium sulfate (Na.sub.2SO.sub.4) and the solvent was eliminated by evaporation at reduced pressure. A crude oil was obtained, which was purified by means of flash chromatography on silica gel, using as eluent a mixture of dichloromethane (CH.sub.2Cl.sub.2)/ethyl phosphate (ETP) (6:4, v/v), obtaining 0.50 g (yield 36%) of 4-hexyloxy-N,N-bis-(4-(3,4-ethylenedioxythien-5-yl)aniline (16), as a yellow solid.
(58) Said 4-hexyloxy-N,N-bis-(4-(3,4-ethylenedioxy-thien-5-yl)aniline (16) was characterized by means of .sup.1H-NMR (500 MHz; CDCl.sub.3; Me.sub.4Si) obtaining the following spectrum: .sub.H 7.54 (4 H, d, J 8.8), 7.07 (2 H, d, J 8.9), 7.03 (4 H, d, J 8.8), 6.83 (2 H, d, J 8.9), 6.24 (2 H, s), 4.31-4.27 (4 H, m), 4.26-4.22 (4 H, m), 3.94 (2 H, t, J 6.5), 1.82-1.74 (2 H, m), 1.50-1.42 (2 H, m), 1.38-1.32 (4 H, m), 0.91 (3 H, t, J 7.1).
Synthesis of 4-hexyloxy-N,N-bis-(4-((3,4-ethylene-dioxythien-5-yl)thieno[3,2-b]thien-5-yl)phenyl)aniline (17)
(59) 0.50 g (0.80 mmoles) of 4-hexyloxy-N,N-bis-(4-(3,4-ethylenedioxythien-5-yl)aniline (16) obtained as described above and 10 ml of dimethylformamide (DMF), were introduced into a 50 ml flask. The solution obtained was cooled to 0 C. with an ice bath and a solution of N-bromosuccinimide (NBS) (0.28 g, 1.6 mmoles) in 5 ml of dimethylformamide (DMF) was then slowly added dropwise. At the end of the dripping, the reaction mixture was heated to room temperature (25 C.) and left under stirring, for 30 minutes. The reaction mixture was then poured into 75 ml of water obtaining the precipitation of a yellow solid which was recovered by filtration at reduced pressure and immediately transferred into a 50 ml microwave test-tube, previously anhydrified and maintained under a flow of nitrogen (N.sub.2) into which 20 ml of a mixture of methanol (MeOH)/toluene (1:1 v/v), 0.86 g (3.2 mmoles) of 5-(4,4,4,5,5-tetramethyl-1,3,2-dioxaborolane)-thieno[3,2-b]thiophene [obtained as described by Alesi S. et al., in Green Chemistry (2008), Vol. 10, pages 517-523], 0.092 g (0.08 mmoles) of 1,1-bis(diphenyl-phosphine)ferrocene-palladium(II)-dichloride complexed with dichloromethane [Pd(dppf)Cl.sub.2] and 1.10 g (8.0 mmoles) of potassium carbonate (K.sub.2CO.sub.3), were subsequently added. The test-tube was then sealed and heated with microwaves to 70 C., 50 W, for 20 minutes. 20 ml of dichloromethane (CH.sub.2Cl.sub.2) were then added and the whole mixture was poured into a 250 ml flask containing 100 ml of a saturated aqueous solution of ammonium chloride (NH.sub.4Cl) and extracted with dichloromethane (CH.sub.2Cl.sub.2) (320 ml). The organic phase obtained was dried on sodium sulfate (Na.sub.2SO.sub.4) and the solvent was eliminated by evaporation at reduced pressure. A crude oil was obtained, which was purified by means of flash chromatography on silica gel, using as eluent a mixture of ethyl phosphate (ETP)/dichloromethane (CH.sub.2Cl.sub.2) (95:5, v/v), obtaining 0.135 g (yield 19%) of 4-hexyloxy-N,N-bis-(4-((3,4-ethylene-dioxythien-5-yl)thieno[3,2-b]thien-5-yl)-phenyl)aniline (17), as a yellow solid.
(60) Said 4-hexyloxy-N,N-bis-(4-((3,4-ethylene-dioxy-thien-5-yl)thieno[3,2-b]thien-5-yl)-phenyl)aniline (17) was characterized by means of .sup.1H-NMR (500 MHz; DMSO-d.sub.6; Me.sub.4Si) obtaining the following spectrum: .sub.H 7.63 (2 H, d, J 5.2), 7.59 (4 H, d, J 8.8), 7.59 (2 H, s), 7.42 (2 H, d, J 5.2), 7.07 (2 H, d, J 8.9), 7.02 (4 H, d, J 8.8), 6.96 (2 H, d, J 8.9), 4.48-4.44 (4 H, m), 4.43-4.39 (4 H, m), 3.97 (2 H, t, J 6.4), 1.76-1.69 (2 H, m), 1.47-1.40 (2 H, m), 1.36-1.30 (4 H, m), 0.90 (3 H, t, J 7.1).
Synthesis of 4-hexyloxy-N,N-bis-(4-(5-formyl-(3,4-ethylenedioxythien-5-yl)thieno[3,2-b]thien-5-yl)phenyl)aniline (18)
(61) 0.076 g (1.0 mmoles) of dimethyl formamide (DMF) were introduced into a 100 ml flask, previously anhydrified and maintained under a flow of nitrogen (N.sub.2), and subsequently, after cooling to a temperature of 10 C., 0.15 g (1.0 mmole) of phosphorous oxychloride (POCl.sub.3) were slowly added dropwise: the formation of a vitreous white solid was observed and after 30 minutes, 5 ml of dimethylformamide (DMF) were added. After the complete dissolution of the reaction mixture, 0.135 g (0.15 mmoles) of 4-hexyloxy-N,N-bis-(4-((3,4-ethylene-dioxy-thien-5-yl)thieno[3,2-b]thien-5-yl)-phenyl)aniline (17), obtained as described above, dissolved in 20 ml of dimethylformamide (DMF), were added. The reaction mixture was left under stirring, at 70 C., for 4 hours. The reaction was then quenched by adding 40 ml of a saturated aqueous solution of potassium carbonate (K.sub.2CO.sub.3) and the whole mixture was left, under stirring, for 1 hour and then extracted with ethyl acetate (AcOEt) (330 ml). The organic phase obtained was washed with water (220 ml) and dried on sodium sulfate (Na.sub.2SO.sub.4). After eliminating the solvent by evaporation at reduced pressure, a crude oil was obtained, which was purified by means of flash chromatography on silica gel using as eluent, a mixture of dichloromethane (CH.sub.2Cl.sub.2)/ethyl acetate (AcOEt) (95:5 v/v), obtaining 0.13 g (yield 87%) of 4-hexyloxy-N,N-bis-(4-(5-formyl-(3,4-ethylenedioxythien-5-yl)thieno-[3,2-b]thien-5-yl)phenyl)aniline (18), as a dark orange solid.
(62) Said 4-hexyloxy-N,N-bis-(4-(5-formyl-(3,4-ethylenedioxythien-5-yl)thieno-[3,2-b]thien-5-yl)-phenyl)aniline (18) was characterized by means of .sup.1H-NMR (500 MHz; DMSO-d.sub.6; Me.sub.4Si) obtaining the following spectrum: .sub.H 9.94 (2 H, s), 8.34 (2 H, s), 7.69 (2 H, s), 7.62 (4 H, d, J 8.8), 7.08 (2 H, d, J 8.9), 7.03 (4 H, d, J 8.8), 6.96 (2 H, d, J 8.9), 4.53-4.48 (4 H, m), 4.45-4.41 (4 H, m), 3.97 (2 H, t, J 6.4), 1.76-1.69 (2 H, m), 1.47-1.40 (2 H, m), 1.36-1.30 (4 H, m), 0.90 (3 H, t, J 7.1).
Synthesis of the Compound (F5)
(63) 0.130 g (0.13 mmoles) of 4-hexyloxy-N,N-bis-(4-(5-formyl-(3,4-ethylenedioxythien-5-yl)thieno-[3,2-b]-thien-5-yl)phenyl)aniline (18), obtained as described above, and 10 ml of chloroform (CHCl.sub.3) were introduced into a 50 ml flask: 0.11 g (1.3 mmoles) of 2-cyanoacetic acid were then added to the solution obtained. The reaction mixture was cooled to 0 C. with an ice bath and a solution of piperidine (0.13 g, 1.5 mmoles) in 5 ml of chloroform (CHCl.sub.3) was subsequently slowly added dropwise. At the end of the dripping, the reaction mixture was heated to the reflux temperature of the solvent, for 10 hours. The reaction mixture was then left to cool to room temperature (25 C.) and the solvent was eliminated by evaporation at reduced pressure, obtaining a dark orange crude oil which was dissolved in 50 ml of water and treated with 20 ml of an aqueous solution of hydrochloric acid at 10%: in this phase, the formation of a dark precipitate was observed, which was recovered by filtration at reduced pressure, washed with water (215 ml) and dried under vacuum obtaining 0.07 g (yield 46%) of the compound (F5) as a purple solid, having a melting point >250 C.
(64) Said compound (F5) was characterized by means of .sup.1H-NMR (500 MHz; DMSO-d.sub.6; Me.sub.4Si) obtaining the following spectrum: .sub.H 8.19 (2 H, s), 8.02 (2 H, s), 7.68 (2 H, s), 7.62 (4 H, d, J 8.8), 7.08 (2 H, d, J 8.9), 7.03 (4 H, d, J 8.8), 6.97 (2 H, d, J 8.9), 4.53-4.47 (4 H, m), 4.45-4.39 (4 H, m), 3.97 (2 H, t, J 6.4), 1.76-1.69 (2 H, m), 1.47-1.40 (2 H, m), 1.36-1.30 (4 H, m), 0.90 (3 H, t, J 7.1).
Example 6
Preparation of the Compound F6
(65) ##STR00060##
(66) The compound (F6) was synthesized according to the following Scheme 6:
(67) ##STR00061##
wherein: (i) indicates trimethylsilylacetylene, bis(triphenylphosphine)palladium(II)dichloride [Pd(PPh.sub.3).sub.2Cl.sub.2], triphenylphosphine (PPh.sub.3), copper iodide (CuI), triethylamine (Et.sub.3N), potassium carbonate (K.sub.2CO.sub.3), methanol (MeOH); (ii) indicates 5-bromo-2-thiophencarbaldehyde, bis(triphenylphosphine)-palladium(II)dichloride [Pd (PPh.sub.3).sub.2Cl.sub.2], triphenyl-phosphine (PPh.sub.3), copper iodide (CuI), triethylamine (Et.sub.3N), argon (Ar); (iii) indicates 2-cyanoacetic acid, piperidine, chloroform (CHCl.sub.3).
Synthesis of 4-hexyloxy-N,N-bis-(4-(ethin-2-yl)phenyl)-aniline (19)
(68) 0.66 g (1.31 mmoles) of 4-hexyloxy-N,N-bis-(4-bromophenyl)aniline (15) obtained as described in Example 5, 2.57 g (26.2 mmoles) of trimethylsilylacetylene, 0.09 g (0.13 mmoles) of bis(triphenylphosphine)palladium(II)dichloride [Pd(PPh.sub.3).sub.2Cl.sub.2], 0.03 g (0.13 mmoles) of triphenylphosphine (PPh.sub.3), 0.025 g (0.13 mmoles) of copper iodide (CuI) and 10 ml of triethylamine (Et.sub.3N), were introduced into a 100 ml flask, previously anhydrified and maintained under a flow of nitrogen (N.sub.2). The reaction mixture was put under stirring and heated to 75 C., for 29 hours. The reaction was then quenched by adding 50 ml of diethyl ether (Et.sub.2O) and the whole mixture was poured into a 500 ml flask containing 150 ml of a saturated aqueous solution of ammonium chloride (NH.sub.4Cl). The whole mixture was kept under magnetic stirring, for 30 minutes, at room temperature (25 C.) and then extracted with diethyl ether (Et.sub.2O) (4100 ml). The organic phase obtained was dried on sodium sulfate (Na.sub.2SO.sub.4) and the solvent was eliminated by evaporation at reduced pressure, obtaining a dark yellow liquid which was treated with 100 ml of a saturated solution of potassium carbonate (K.sub.2CO.sub.3) in methanol (MeOH): the whole mixture was kept, under stirring, at room temperature (25 C.), for 24 hours, and then subjected to filtration. The organic phase obtained was washed with water (4200 ml) and dried on sodium sulfate (Na.sub.2SO.sub.4) and the solvent was eliminated by evaporation. A crude oil was obtained which was purified by flash chromatography on silica gel, using as eluent a mixture of ethyl phosphate (ETP)/dichloromethane (CH.sub.2Cl.sub.2) (95:5 v/v), obtaining 0.075 g (yield 15%) of 4-hexyloxy-N,N-bis-(4-(ethin-2-yl)phenyl)aniline (19), as a colourless oil.
(69) Said 4-hexyloxy-N,N-bis-(4-(ethin-2-yl)phenyl)-aniline (19) was characterized by means of .sup.1H-NMR (500 MHz; CDCl.sub.3; Me.sub.4Si) obtaining the following spectrum: .sub.H 7.33 (4 H, d, J 8.7), 7.04 (2 H, d, J 8.9), 6.96 (4 H, d, J 8.7), 6.85 (2 H, d, J 8.9), 3.94 (2 H, t, J 6.6), 3.02 (2 H, s), 1.82-1.75 (2 H, m), 1.51-1.43 (2 H, m), 1.37-1.32 (4 H, m), 0.91 (3 H, t, J 7.0).
Synthesis of 4-hexyloxy-N,N-bis-{4-[(5-formylthieno-2-yl)ethin-2-yl]phenyl}aniline (20)
(70) 0.11 g (0.28 mmoles) of 4-hexyloxy-N,N-bis-(4-(ethin-2-yl)phenyl)aniline (19) obtained as described above, 0.57 g (5.60 mmoles) of 5-bromo-2-thiophencarbaldehyde [obtained as described by Zhan H. et al., in Macromolecules (2011), Vol. 44, pages 5155-5167], 0.02 g (0.03 mmoles) of bis(triphenylphosphine)palladium(II)dichloride [Pd(PPh.sub.3).sub.2Cl.sub.2], 0.007 g (0.03 mmoles) of triphenylphosphine (PPh.sub.3), 0.005 g (0.03 mmoles) of copper iodide (CuI) and 10 ml of triethylamine (Et.sub.3N), were introduced into a 100 ml flask, previously anhydrified and maintained under a flow of nitrogen (N.sub.2): the reaction mixture appeared orange-coloured and was kept, under stirring, at room temperature (25 C.), for 24 hours. The reaction was then quenched by adding 10 ml of water and subsequently 70 ml of diethyl ether (Et.sub.2O) and the whole mixture was poured into a 500 ml flask containing 150 ml of a saturated aqueous solution of ammonium chloride (NH.sub.4Cl): the whole mixture was kept, under stirring, at room temperature (25 C.), for 24 hours and then subjected to filtration. The organic phase obtained was washed with water (4200 ml) and dried on sodium sulfate (Na.sub.2SO.sub.4) and the solvent was eliminated by evaporation at reduced pressure. A crude oil was obtained which was purified by flash chromatography on silica gel, using as eluent a mixture of ethyl phosphate (ETP)/dichloromethane (CH.sub.2Cl.sub.2) (1:9 v/v), obtaining 0.10 g (yield 57%) of 4-hexyloxy-N,N-bis-{4-[(5-formylthieno-2-yl)ethin-2-yl]phenyl}aniline (20) as an orange oil.
(71) Said 4-hexyloxy-N,N-bis-{4-[(5-formylthieno-2-yl)-ethin-2-yl]phenyl}aniline (20) was characterized by means of .sup.1H-NMR (500 MHz; CDCl.sub.3; Me.sub.4Si) obtaining the following spectrum: .sub.H 9.85 (2 H, s), 7.66 (2 H, d, J 3.9), 7.39 (2 H, d, J 8.8), 7.27 (2 H, d, J 3.9), 7.07 (2 H, d, J 8.9), 7.03 (2 H, d, J 8.8), 6.89 (2 H, d, J 8.9), 3.95 (2 H, t, J 6.7), 1.82-1.75 (2 H, m), 1.51-1.43 (2 H, m), 1.37-1.32 (4 H, m), 0.91 (3 H, t, J 7.0).
Synthesis of the Compound (F6)
(72) 0.10 g (0.16 mmoles) of 4-hexyloxy-N,N-bis-{4-[(5-formylthieno-2-yl)-ethin-2-yl]phenyl}aniline (20) obtained as described above and 10 ml of chloroform (CHCl.sub.3), where introduced into a 50 ml flask, previously anhydrified and maintained under a flow of nitrogen (N.sub.2): a solution of cyanoacetic acid (0.28 g, 3.26 mmoles) and piperidine (0.03 g, 3.59 mmoles) in 5 ml of chloroform (CHCl.sub.3) was then slowly added dropwise to the solution obtained. At the end of the dripping, the reaction mixture was heated to the reflux temperature of the solvent, for 12 hours: in this phase, the solution passed from light orange to a dark red colour. The reaction mixture was then quenched by adding 1 ml of water and the solvent was eliminated by evaporation at reduced pressure, obtaining a dark red solid which was then suspended in 10 ml of water. After cooling the suspension obtained to 0 C. with an ice bath, 10 ml of an aqueous solution of hydrochloric acid (HCl) at 10% were added: the whole mixture was kept at 0 C., under stirring, for 1 hour. The solid formed was subsequently recovered by filtration with a Hirsh filter, washed with water (310 ml) and dried under vacuum obtaining 0.08 g (yield 69%) of the compound (F6), as a dark purple solid.
(73) Said compound (F6) was characterized by means of .sup.1H-NMR (500 MHz; DMSO-d.sub.6; Me.sub.4Si) obtaining the following spectrum: .sub.H 8.45 (2 H, s), 7.95 (2 H, d, J 3.9), 7.53 (2 H, d, J 3.9), 7.52 (4 H, d, J 8.9), 7.13 (2 H, d, J 8.9), 7.04-6.98 (6 H, m), 3.98 (2 H, t, J 6.4), 1.77-1.67 (2 H, m), 1.47-1.37 (2 H, m), 1.34-1.29 (4 H, m), 0.89 (3 H, t, J=7.1).
(74) Said compound (F6) was also characterized by means of .sup.13C-NMR obtaining the following spectrum: .sub.C (125.77 MHz; DMSO-d.sub.6; Me.sub.4Si) 138.25, 137.04, 133.36, 130.74, 129.17, 122.33, 117.23, 116.48, 114.52, 99.09, 82.22, 68.22, 31.46, 29.15, 25.66, 22.54, 14.37.
Example 7
Preparation of the Compound (F7)
(75) ##STR00062##
(76) The compound (F7) was synthesized according to the following Scheme 7:
(77) ##STR00063##
wherein: (i) indicates 5-(4,4,4,5,5-tetramethyl-1,3,2-dioxaborolan)thieno[3,2-b]thiophene, 1,1-bis(diphenyl-phosphine)ferrocene-palladium(II)dichloride complexed with dichloromethane [Pd(dppf)Cl.sub.2], potassium carbonate (K.sub.2CO.sub.3), methanol (MeOH), toluene; (ii) indicates dimethylformamide (DMF), phosphorous oxychloride (POCl.sub.3); (iii) indicates N-bromosuccinimide (NBS), dimethylformamide (DMF), (iv) indicates 5-hexyl-2-thiophene boronic acid pinacol ester, 1,1-bis(diphenyl-phosphine)ferrocene-palladium(II)dichloride complexed with dichloromethane [Pd(dppf)Cl.sub.2], potassium carbonate (K.sub.2CO.sub.3), methanol (MeOH), toluene; (v) indicates 2-cyanoacetic acid, piperidine, chloroform (CHCl.sub.3).
Synthesis of N,N-bis-(4-(thieno[3,2-b]thien-5-yl)-phenyl)aniline (22)
(78) 6 ml of a mixture of methanol (MeOH)/toluene (1:1 v/v), 0.44 g (1.0 mmoles) of N,N-bis-(4-bromophenyl)aniline (21) [obtained as described by D. Sahu et al., in Journal of Materials Chemistry (2012), Vol. 22, pages 7945-7953], 0.67 g (2.5 mmoles) of 5-(4,4,4,5,5-tetramethyl-1,3,2-dioxaborolane)-thieno[3,2-b]thiophene [obtained as described by Alesi S. et al., in Green Chemistry (2008), Vol. 10, pages 517-523], 0.08 g (0.10 mmoles) of 1,1-bis(diphenylphosphine)ferrocene-palladium(II)dichloride complexed with dichloromethane [Pd(dppf)Cl.sub.2] and 0.69 g (5.0 mmoles) of potassium carbonate (K.sub.2CO.sub.3), were introduced into a 30 ml microwave test-tube.
(79) The test-tube was then sealed and heated with microwaves to 70 C., 50 W, for 40 minutes. 20 ml of dichloromethane (CH.sub.2Cl.sub.2) were then added and the whole mixture was poured into 50 ml of a saturated aqueous solution of ammonium chloride (NH.sub.4Cl) and extracted with dichloromethane (CH.sub.2Cl.sub.2) (320 ml). The organic phase obtained was washed with water (215 ml) and dried on sodium sulfate (Na.sub.2SO.sub.4). After eliminating the solvent by evaporation at reduced pressure, a crude oil was obtained, which was purified by means of flash chromatography on silica gel, using as eluent a mixture of n-hexane/dichloromethane (CH.sub.2Cl.sub.2) (7:3, v/v), obtaining 0.20 g (yield 40%) of N,N-bis-(4-(thieno[3,2-b]thien-5-yl)-phenyl)aniline (22), as a yellow solid.
(80) Said N,N-bis-(4-(thieno[3,2-b]thien-5-yl)-phenyl)-aniline (22) was characterized by means of .sup.1H-NMR (500 MHz; CDCl.sub.3; Me.sub.4Si) obtaining the following spectrum: .sub.H 7.51 (4 H, d, J 8.6), 7.41 (2 H, s), 7.34 (2 H, d, J 5.2), 7.30 (1 H, t, J 8.0), 7.24 (2 H, d, J 5.2), 7.17 (2 H, t, J 8.3), 7.13 (4 H, d, J 8.6).
Synthesis of N,N-bis-(4-(5-formyl-thieno[3,2-b]thien-5-yl)phenyl)aniline (23)
(81) 0.07 g (0.90 mmoles) of dimethyl formamide (DMF) were introduced into a 100 ml flask, previously anhydrified and maintained under a flow of nitrogen (N.sub.2), and subsequently, after cooling to a temperature of 10 C., 0.14 g (0.90 mmoles) of phosphorous oxychloride (POCl.sub.3) were slowly added dropwise: the formation of a vitreous white solid was observed and after 30 minutes, 10 ml of dimethylformamide (DMF) were added. After the complete dissolution of the reaction mixture, 0.20 g (0.39 mmoles) of N,N-bis-(4-(thieno[3,2-b]thien-5-yl)-phenyl)-aniline (22), obtained as described above, dissolved in 15 ml of dimethylformamide (DMF), were added. The reaction mixture was left, under stirring, at 70 C., for 4 hours. The reaction was then quenched by adding 20 ml of a saturated aqueous solution of sodium acetate (AcONa) and the whole mixture was left, under stirring, for 1 hour and then extracted with dichloromethane (CH.sub.2Cl.sub.2) (315 ml). The organic phase obtained was washed with water (215 ml) and dried on sodium sulfate (Na.sub.2SO.sub.4). After eliminating the solvent by evaporation at reduced pressure, 0.16 g (yield 72%) of N,N-bis-(4-(5-formyl-thieno[3,2-b]thien-5-yl)phenyl)aniline (23) were obtained, as a dark orange solid.
(82) Said N,N-bis-(4-(5-formyl-thieno[3,2-b]thien-5-yl)-phenyl)aniline (23) was characterized by means of .sup.1H-NMR (500 MHz; CDCl.sub.3; Me.sub.4Si) obtaining the following spectrum: .sub.H 9.97 (2 H, s), 8.39 (2 H, s), 7.94 (2 H, s), 7.76 (1 H, t, J 8.5), 7.72 (4 H, d, J 8.7), 7.42 (2 H, t, J 8.1), 7.18 (2 H, d, J 7.5), 7.13 (4 H, d, J 8.7).
Synthesis of 4-bromo-N,N-bis-(4-(5-formyl-thieno[3,2-b]thien-5-yl)phenyl)aniline (24)
(83) 0.16 g (0.28 mmoles) of N,N-bis-(4-(5-formyl-thieno[3,2-b]thien-5-yl)phenyl)aniline (23) obtained as described above and 10 ml of dimethylformamide (DMF), were introduced into a 50 ml flask and, after cooling, the solution to 0 C. with an ice bath, a solution of N-bromosuccinimide (NBS) (0.10 g, 0.56 mmoles) in 5 ml of dimethylformamide (DMF) were then slowly added dropwise. At the end of the dripping, the reaction mixture was heated to room temperature (25 C.) and kept, under stirring, for 16 hours. The reaction mixture was then poured into a 250 ml flask containing 75 ml of water and 20 ml of diethyl ether (Et.sub.2O) and was extracted with diethyl ether (Et.sub.2O) (315 ml). The organic phase obtained was dried on sodium sulfate (Na.sub.2SO.sub.4) and the solvent was eliminated by evaporation at reduced pressure, obtaining 0.14 g (yield 84%) of 4-bromo-N,N-bis-(4-(5-formyl-thieno[3,2-b]thien-5-yl)phenyl)aniline (24) as a brown solid.
(84) Said 4-bromo-N,N-bis-(4-(5-formyl-thieno[3,2-b]thien-5-yl)phenyl)aniline (24) was characterized by means of .sup.1H-NMR (500 MHz; CDCl.sub.3; Me.sub.4Si) obtaining the following spectrum: .sub.H 9.95 (2 H, s), 7.91 (2 H, s), 7.56 (4 H, d, J 8.2), 7.47 (2 H, s), 7.44 (2 H, d, J 8.6), 7.15 (4 H, d, J 8.5), 7.06 (2 H, d, J 8.7).
Synthesis of 4-(5-hexyl-2-thieno)-N,N-bis-(4-(5-formyl-thieno[3,2-b]thien-5-il)phenyl)aniline (25)
(85) 6 ml of a mixture of methanol (MeOH)/toluene (1:1 v/v), 0.10 g (0.15 mmoles) of 4-bromo-N,N-bis-(4-(5-formyl-thieno[3,2-b]thien-5-yl)phenyl)aniline (24) obtained as described above, 0.09 g (0.30 mmoles) of 5-hexyl-2-thiophene boronic acid pinacol ester, 0.03 g (0.03 mmoles) of 1,1-bis(diphenylphosphine)ferrocene-palladium(II)dichloride complexed with dichloromethane [Pd(dppf)Cl.sub.2] and 0.11 g (0.80 mmoles) of potassium carbonate (K.sub.2CO.sub.3), were introduced into a 50 ml microwave test-tube. The test-tube was then sealed and heated with microwaves to 70 C., 50 W, for 40 minutes. 20 ml of dichloromethane (CH.sub.2Cl.sub.2) were then added and the whole mixture was poured into 50 ml of a saturated aqueous solution of ammonium chloride (NH.sub.4Cl) and extracted with dichloromethane (CH.sub.2Cl.sub.2) (320 ml). The organic phase obtained was washed with water (215 ml) and dried on sodium sulfate (Na.sub.2SO.sub.4). After eliminating the solvent by evaporation at reduced pressure, a crude oil was obtained, which was purified by means of flash chromatography on silica gel, using as eluent a mixture of dichloromethane (CH.sub.2Cl.sub.2), obtaining 0.05 g (yield 46%) of 4-(5-hexyl-2-thieno)-N,N-bis-(4-(5-formyl-thieno[3,2-b]thien-5-il)phenyl)-aniline (25) as an orange solid.
(86) Said 4-(5-hexyl-2-thieno)-N,N-bis-(4-(5-formyl-thieno[3,2-b]thien-5-il)phenyl)-aniline (25) was characterized by means of .sup.1H-NMR (500 MHz; CDCl.sub.3; Me.sub.4Si) obtaining the following spectrum: .sub.H 9.94 (2 H, s), 7.84 (2 H, s), 7.56 (4 H, d, J 8.6), 7.52 (2 H, d, J 8.5), 7.46 (2 H, s), 7.18 (4 H, d, J 8.6), 7.15 (2 H, d, J 8.5), 7.09 (1 H, d, J 3.5), 6.74 (1 H, d, J 3.0), 2.82 (2 H, t, J 7.6), 1.70 (2 H, quintet, J 7.5), 1.39 (2 H, quintet, J 6.3), 1.35-1.30 (4 H, m), 0.90 (3 H, t, J 6.7).
Synthesis of the Compound (F7)
(87) 0.05 g (0.07 mmoles) of 4-(5-hexyl-2-thieno)-N,N-bis-(4-(5-formyl-thieno[3,2-b]thien-5-il)phenyl)-aniline (25) obtained as described above and 10 ml of chloroform (CHCl.sub.3) where introduced into a 50 ml flask, previously anhydrified and maintained under a flow of nitrogen (N.sub.2): a solution of cyanoacetic acid (0.06 g, 0.70 mmoles) and piperidine (0.07 g, 0.80 mmoles) in 5 ml of chloroform (CHCl.sub.3) were then slowly added dropwise to the solution obtained. At the end of the dripping, the reaction mixture was heated to the reflux temperature of the solvent, for 12 hours: in this phase, the solution passed from light orange to a dark red colour. The reaction mixture was quenched by adding 1 ml of water and the solvent was eliminated by evaporation at reduced pressure, obtaining a dark red solid which was then suspended in 10 ml of water. After cooling the suspension obtained to 0 C. with an ice bath, 10 ml of an aqueous solution of hydrochloric acid (HCl) at 10% were added: the whole mixture was kept at 0 C., under stirring, for 1 hour. The solid formed was subsequently recovered by filtration with a Hirsh filter, washed with water (310 ml) and dried under vacuum obtaining 0.04 g (yield 65%) of the compound (F7), as a dark purple solid.
(88) Said compound (F7) was characterized by means of .sup.1H-NMR (500 MHz; DMSO-d.sub.6; Me.sub.4Si) obtaining the following spectrum: .sub.H 8.47 (2 H, s), 8.25 (2 H, s), 7.97 (2 H, s), 7.72 (4 H, d, J 8.7), 7.59 (2 H, d, J 8.6), 7.27 (1 H, d, J 3.5), 7.16 (4 H, d, J 8.7), 7.15 (2 H, d, J 8.5), 6.84 (1 H, d, J 3.5), 2.79 (2 H, t, J 7.5), 1.65 (2 H, quintet, J 7.5), 1.35 (2 H, quintet, J 6.3), 1.32-1.28 (4 H, m), 0.87 (3 H, t, J 6.7).
Example 8
Preparation of the Compound (F8)
(89) ##STR00064##
(90) The compound (F8) was synthesized according to the following Scheme 8:
(91) ##STR00065##
wherein: (i) indicates 5-hexyl-2,2-bithiophene-5 boronic acid pinacol ester, 1,1-bis(diphenyl-phosphine)ferrocene-palladium(II)dichloride complexed with dichloromethane [Pd(dppf)Cl.sub.2], potassium carbonate (K.sub.2CO.sub.3), methanol (MeOH), toluene; (ii) indicates 2-cyanoacetic acid, piperidine, chloroform (CHCl.sub.3).
Synthesis of 4-(5-hexyl-2,2-bithien-5-yl)-N,N-bis-(4-(5-formyl-thieno[3,2-b]thien-5-yl)phenyl)aniline (26)
(92) 6 ml of a mixture of methanol (MeOH)/toluene (1:1 v/v), 0.05 g (0.08 mmoles) of 4-bromo-N,N-bis-(4-(5-formyl-thieno[3,2-b]thien-5-yl)phenyl)aniline (24) obtained as described in Example 7, 0.07 g (0.30 mmoles) of 5-hexyl-2,2-bithiophene-5 boronic acid pinacol ester, 0.01 g (0.01 mmoles) of 1,1-bis(diphenylphosphine)ferrocene-palladium(II)dichloride complexed with dichloromethane [Pd(dppf)Cl.sub.2] and 0.05 g (0.40 mmoles) of potassium carbonate (K.sub.2CO.sub.3), were introduced into a 50 ml microwave test-tube. The test-tube was then sealed and heated with microwaves to 70 C., 50 W, for 40 minutes. 20 ml of dichloromethane (CH.sub.2Cl.sub.2) were then added and the whole mixture was poured into 50 ml of a saturated aqueous solution of ammonium chloride (NH.sub.4Cl) and extracted with dichloromethane (CH.sub.2Cl.sub.2) (320 ml). The organic phase obtained was washed with water (215 ml) and dried on sodium sulfate (Na.sub.2SO.sub.4). After eliminating the solvent by evaporation at reduced pressure, a crude oil was obtained, which was purified by means of flash chromatography on silica gel, using as eluent a mixture of dichloromethane (CH.sub.2Cl.sub.2), obtaining 0.03 g (yield 50%) of 4-(5-hexyl-2,2-bithien-5-yl)-N,N-bis-(4-(5-formyl-thieno[3,2-b]thien-5-yl)phenyl)aniline (26) as a dark orange solid.
(93) Said 4-(5-hexyl-2,2-bithien-5-yl)-N,N-bis-(4-(5-formyl-thieno[3,2-b]thien-5-yl)phenyl)aniline (26) was characterized by means of .sup.1H-NMR (500 MHz; CDCl.sub.3; Me.sub.4Si) obtaining the following spectrum: .sub.H 9.95 (2 H, s), 7.90 (2 H, s), 7.57 (4 H, d, J 8.7), 7.54 (2 H, d, J 8.7), 7.47 (2 H, s), 7.19 (4 H, d, J 8.7), 7.16 (1 H, d, J 3.7), 7.15 (2 H, d, J 8.7), 7.06 (1 H, d, J 3.6), 7.00 (1 H, d, J 3.5), 6.69 (1 H, d, J 3.5), 2.79 (2 H, t, J 7.6), 1.69 (2 H, quintet, J 7.5), 1.42-1.36 (2 H, m), 1.34-1.29 (4 H, m), 0.89 (3 H, t, J 7.0).
Synthesis of the Compound (F8)
(94) 0.03 g (0.04 mmoles) of 4-(5-hexyl-2,2-bithien-5-yl)-N,N-bis-(4-(5-formyl-thieno[3,2-b]thien-5-yl)-phenyl)aniline (26) obtained as described above and 10 ml of chloroform (CHCl.sub.3), where introduced into a 50 ml flask, previously anhydrified and maintained under a flow of nitrogen (N.sub.2): a solution of cyanoacetic acid (0.03 g, 0.40 mmoles) and piperidine (0.04 g, 0.50 mmoles) in 5 ml of chloroform (CHCl.sub.3) was then slowly added dropwise to the solution obtained. At the end of the dripping, the reaction mixture was heated to the reflux temperature of the solvent, for 12 hours: in this phase, the solution passed from light orange to a dark red colour. The reaction mixture was quenched by adding 1 ml of water and the solvent was eliminated by evaporation at reduced pressure, obtaining a dark red solid which was then suspended in 10 ml of water. After cooling the suspension obtained to 0 C. with an ice bath, 10 ml of an aqueous solution of hydrochloric acid (HCl) at 10% were added: the whole mixture was kept at 0 C., under stirring for 1 hour. The solid formed was subsequently recovered by filtration with a Hirsh filter, washed with water (310 ml) and dried under vacuum obtaining 0.03 g (yield 65%) of the compound (F8), as a dark purple solid.
(95) Said compound (F8) was characterized by means of .sup.1H-NMR (500 MHz; DMSO-d.sub.6; Me.sub.4Si) obtaining the following spectrum: .sub.H 8.56 (2 H, s), 8.31 (2 H, s), 7.99 (2 H, s), 7.74 (4 H, d, J 8.6), 7.66 (2 H, d, J 8.6), 7.42 (1 H, d, J 3.7), 7.22 (1 H, d, J 3.7), 7.20-7.12 (7 H, m), 6.82 (1 H, d, J 3.4), 2.79 (2 H, t, J 7.5), 1.65 (2 H, quintet, J 7.5), 1.35 (2 H, quintet, J 6.3), 1.32-1.28 (4 H, m), 0.87 (3 H, t, J 6.7).
Example 9
Synthesis of the Compound (F9)
(96) ##STR00066##
(97) The compound (F9) was synthesized according to the following Scheme 9:
(98) ##STR00067##
wherein: (i) indicates 4,4,5,5-tetramethyl-2-(2,4-dihexyloxyphenyl)-1,3,2-dioxaborolane, 1,1-bis(diphenylphosphine)ferrocene-palladium(II)dichloride complexed with dichloromethane [Pd(dppf)Cl.sub.2], potassium carbonate (K.sub.2CO.sub.3), methanol (MeOH), toluene; (ii) indicates 2-cyanoacetic acid, piperidine, chloroform (CHCl.sub.3).
Synthesis of 4-(2,4-dihexyloxyphenyl)-N,N-bis-(4-(5-formyl-thieno[3,2-b]thien-5-yl)phenyl)aniline (27)
(99) 6 ml of a mixture of methanol (MeOH)/toluene (1:1 v/v), 0.10 g (0.15 mmoles) of 4-bromo-N,N-bis-(4-(5-formyl-thieno[3,2-b]thien-5-yl)phenyl)aniline (24) obtained as described in Example 7, 0.12 g (0.30 mmoles) of 4,4,5,5-tetramethyl-2-(2,4-dihexyloxyphenyl)-1,3,2-dioxaborolane [obtained as described by Tsao H. N. et al., in ChemSusChem (2011), Vol. 4, pages 591-594], 0.03 g (0.03 mmoles) of 1,1-bis(diphenylphosphine)ferrocene-palladium(II)dichloride complexed with dichloromethane [Pd(dppf)Cl.sub.2] and 0.11 g (0.80 mmoles) of potassium carbonate (K.sub.2CO.sub.3), were introduced into a 50 ml microwave test-tube. The test-tube was then sealed and heated with microwaves to 70 C., 50 W, for 40 minutes. 20 ml of dichloromethane (CH.sub.2Cl.sub.2) were then added and the whole mixture was poured into 50 ml of a saturated aqueous solution of ammonium chloride (NH.sub.4Cl) and extracted with dichloromethane (CH.sub.2Cl.sub.2) (320 ml). The organic phase obtained was washed with water (215 ml) and dried on sodium sulfate (Na.sub.2SO.sub.4). After eliminating the solvent by evaporation at reduced pressure, a crude oil was obtained, which was purified by means of flash chromatography on silica gel, using as eluent a mixture of dichloromethane (CH.sub.2Cl.sub.2), obtaining 0.09 g (yield 66%) of 4-(2,4-dihexyloxyphenyl)-N,N-bis-(4-(5-formyl-thieno[3,2-b]thien-5-yl)phenyl)aniline (27) as a dark orange solid.
(100) Said 4-(2,4-dihexyloxyphenyl)-N,N-bis-(4-(5-formyl-thieno[3,2-b]thien-5-yl)phenyl)aniline (27) was characterized by means of .sup.1H-NMR (500 MHz; CDCl.sub.3; Me.sub.4Si) obtaining the following spectrum: .sub.H 9.95 (2 H, s), 7.90 (2 H, s), 7.56 (4 H, d, J 8.7), 7.52 (2 H, d, J 8.6), 7.47 (2 H, s), 7.28 (1 H, s), 7.21 (4 H, d, J 8.7), 7.18 (2 H, d, J 8.6), 6.58-6.54 (2 H, m), 4.02-3.95 (4 H, m), 1.81 (2 H, quintet, J 7.9), 1.76 (2 H, quintet, J 7.9) 1.52-1.45 (2 H, m), 1.52-1.45 (2 H, m), 1.44-1.39 (2 H, m), 1.38-1.34 (4 H, m), 1.33-1.28 (4 H, m), 0.92 (3 H, t, J 6.9), 0.88 (3 H, t, J 7.0).
Synthesis of the Compound (F9)
(101) 0.09 g (0.10 mmoles) of 4-(2,4-dihexyloxyphenyl)-N,N-bis-(4-(5-formyl-thieno[3,2-b]thien-5-yl)phenyl)aniline (27) obtained as described above and 10 ml of chloroform (CHCl.sub.3), where introduced into a 50 ml flask, previously anhydrified and maintained under a flow of nitrogen (N.sub.2): a solution of cyanoacetic acid (0.09 g, 1.0 mmole) and piperidine (0.09 g, 1.1 mmoles) in 5 ml of chloroform (CHCl.sub.3) were then slowly added dropwise to the solution obtained. At the end of the dripping, the reaction mixture was heated to the reflux temperature of the solvent, for 12 hours: in this phase, the solution passed from light orange to a dark red colour. The reaction mixture was then quenched by adding 1 ml of water and the solvent was eliminated by evaporation at reduced pressure, obtaining a dark red solid which was then suspended in 10 ml of water. After cooling the suspension obtained to 0 C. with an ice bath, 10 ml of an aqueous solution of hydrochloric acid (HCl) at 10% were added: the whole mixture was kept at 0 C., under stirring, for 1 hour. The solid formed was subsequently recovered by filtration with a Hirsh filter, washed with water (310 ml) and dried under vacuum obtaining 0.06 g (yield 59%) of the compound (F9), as a dark purple solid.
(102) Said compound (F9) was characterized by means of .sup.1H-NMR (500 MHz; DMSO-d.sub.6; Me.sub.4Si) obtaining the following spectrum: .sub.H 8.46 (2 H, s), 8.23 (2 H, s), 7.95 (2 H, s), 7.69 (4 H, d, J 8.5), 7.49 (2 H, d, J 8.4), 7.23 (1 H, d, J 8.2), 7.16-7.08 (7 H, m), 6.56-6.48 (1 H, m), 4.02-3.95 (4 H, m), 1.81 (2 H, quintet, J 7.9), 1.76 (2 H, quintet, J 7.9) 1.52-1.45 (2 H, m), 1.52-1.45 (2 H, m), 1.44-1.39 (2 H, m), 1.38-1.34 (4 H, m), 1.33-1.28 (4 H, m), 0.92 (3 H, t, J 6.9), 0.88 (3 H, t, J 7.0).
Example 10
Synthesis of the Compound (F10)
(103) ##STR00068##
(104) The compound (F10) was synthesized according to the following Scheme 10:
(105) ##STR00069##
wherein: (i) indicates 2-cyanoacetic acid, piperidine, chloroform (CHCl.sub.3).
Synthesis of the Compound (F10)
(106) 0.29 g (0.50 mmoles) of N,N-bis-(4-(5-formyl-thieno[3,2-b]thien-5-yl)phenyl)aniline (23), obtained as described in Example 7, and 10 ml of chloroform (CHCl.sub.3), where introduced into a 50 ml flask, previously anhydrified and maintained under a flow of nitrogen (N.sub.2): a solution of cyanoacetic acid (0.43 g, 5.0 mmole) and piperidine (0.47 g, 5.5 mmoles) in 5 ml of chloroform (CHCl.sub.3) were then slowly added dropwise to the solution obtained. At the end of the dripping, the reaction mixture was heated to the reflux temperature of the solvent, for 8 hours: in this phase, the solution passed from light orange to a dark red colour. The reaction mixture was then quenched by adding 1 ml of water and the solvent was eliminated by evaporation at reduced pressure, obtaining a dark red solid which was then suspended in 10 ml of water. After cooling the suspension obtained to 0 C. with an ice bath, 10 ml of an aqueous solution of hydrochloric acid (HCl) at 10% were added: the whole mixture was kept at 0 C., under stirring, for 1 hour. The solid formed was subsequently recovered by filtration with a Hirsh filter, washed with water (310 ml) and dried under vacuum obtaining 0.12 g (yield 32%) of the compound (F10), as a dark purple solid.
(107) Said compound (F9) was characterized by means of .sup.1H-NMR (500 MHz; DMSO-d.sub.6; Me.sub.4Si) obtaining the following spectrum: .sub.H 8.57 (2 H, s), 8.33 (2 H, s), 7.98 (2 H, s), 7.71 (4 H, d, J 8.6), 7.69 (1 H, t, J 8.5), 7.42 (2 H, t, J 8.1), 7.19 (2 H, d, J 7.5), 7.14 (4 H, d, J 8.7).
Example 11
Preparation of a Dye Sensitized Solar Cell (DSSC)
(108) The titanium dioxide (TiO.sub.2) electrodes were prepared by the deposition (doctor blade technique) of a colloidal paste containing titanium dioxide (TiO.sub.2) having a dimension of 20 nm (TiO.sub.2 paste DSL 18NR-TDyesol) on FTO conductive glass (Hartford Glass Co., TEC 8, having a thickness of 2.3 mm and a sheet resistance of 6 /cm.sup.2-9 /cm.sup.2), previously cleaned with water and ethanol, treated with a plasma cleaner, at 100 W, for 10 minutes, immersed in a freshly prepared aqueous solution of titanium tetrachloride (TiCl.sub.4) (4.510.sup.2 M), at 70 C., for 30 minutes, and finally washed with ethanol.
(109) After a first drying at 125 C., for 15 minutes, a diffusion reflecting layer containing particles of titanium dioxide (TiO.sub.2) with dimensions >100 nm (Ti-Nanoxide R/SPSolaronix), was deposited (doctor blade technique) on the first layer of titanium dioxide (TiO.sub.2) and sintered at 500 C., for 30 minutes. The glass coated with the film of titanium dioxide (TiO.sub.2) was cooled to room temperature (25 C.) and immersed again in a freshly prepared aqueous solution of titanium tetrachloride (TiCl.sub.4) (4.510.sup.2 M), at 70 C., for 30 minutes, and finally washed with ethanol and sintered again at 500 C., for 30 minutes, obtaining a final thickness of the electrode ranging from 8 m to 12 m.
(110) After sintering, the glass coated with titanium dioxide (TiO.sub.2) film, was cooled to about 80 C.-100 C. and immediately immersed in a solution in dichloromethane (CH.sub.2Cl.sub.2) (510.sup.4 M) of the compound (F1) obtained as described in Example 1, at room temperature (25 C.), for 24 hours. The glass coated with coloured titania was washed with ethanol and dried at room temperature (25 C.), under a flow of nitrogen (N.sub.2).
(111) A Surlyn spacer having a thickness of 50 m (TPS 065093-50Dyesol) was used for sealing the photo-anode obtained as described above and the counter-electrode consisting of platinized FTO glass (Hartford Glass Co., TEC 8, having a thickness of 2.3 mm and a sheet resistance of 6 /cm.sup.2-9 /cm.sup.2). The cell was subsequently filled, through a hole previously made in the platinized FTO glass, with an electrolyte solution having the following composition: N-methyl-N-butylimidazolium iodide (0.6 M), iodine (0.04 M), lithium iodide (LiI) (0.025 M), guanidinium-thiocyanate (0.05 M) and tert-butylpiridine (0.28 M), in a 15:85 mixture (v/v) of valeronitrile and acetonitrile.
(112) The active area of the cell, calculated by means of a microphotograph, was 0.1435 cm.sup.2.
(113) The photovoltaic performance of the cell was measured with a solar simulator (Abet 2000) equipped with a 300 W xenon light source, the light intensity was calibrated with a standard silicon solar cell (VLSI Standard SRC-1000-RTD-KGS), the current-voltage characteristics were obtained by applying an external voltage to the cell and measuring the photocurrent generated with a Keithley 2602A digital multimeter (3A DC, 10A Pulse). The following results were obtained: Voc (open-circuit photovoltage)=0.62 V; FF (Fill Factor)=71.9%; Jsc (short-circuit current density)=14.7 mA/cm.sup.2; (photoelectric transformation efficiency): 6.5%.
Examples 12-20
Preparation of Dye Sensitized Solar Cells (DSSCs)
(114) Following the procedure described in Example 11, Dye Sensitized Solar Cells were prepared using compounds (F2), (F3), (F4), (F5), (F6), (F7), (F8), (F9) and (F10) as dyes, prepared according to what is described in Examples 2, 3, 4, 5, 6, 7, 8, 9 and 10, respectively. The photovoltaic performances were measured on each cell thus obtained, as described in Example 11. The values obtained are indicated in Table 2.
(115) Table 2 indicates in order: the example number (Example), the number referring to the formula of the dye used, the active area of the cell, Voc (open-circuit voltage), FF (Fill Factor), Jsc (short-circuit current density) and (photoelectric transformation efficiency).
(116) TABLE-US-00002 TABLE 2 Area Voc FF Jsc Example Dye (cm.sup.2) (V) (%) (mA/cm.sup.2) (%) 12 (F2) 0.1646 0.59 69.4 12.3 5.1 13 (F3) 0.1231 0.69 73.0 14.9 7.5 14 (F4) 0.1135 0.69 70.4 19.5 9.4 15 (F5) 0.1286 0.62 64.3 16.8 6.7 16 (F6) 0.1027 0.63 70.0 10.5 4.6 17 (F7) 0.1127 0.68 71.1 18.1 8.7 18 (F8) 0.1179 0.66 71.4 14.5 6.8 19 (F9) 0.1115 0.65 70.4 15.5 7.1 20 (F10) 0.1058 0.64 70.7 21.2 9.6