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    • 专利摘要:
    A method for synthesizing π-conjugated materials comprising a step of implementing a synthon comprising a carbazole or fluorene ring.
    公开号:FR3024144A1
    申请号:FR1457308
    申请日:2014-07-28
    公开日:2016-01-29
    发明作者:Martial Degbia；Bruno Schmaltz；Francois Tran-Van
    申请人:Rabelais Francois Universite de Tours；
    IPC主号:
    专利说明:

    [0001] The present invention relates to novel synthons, to a process for their preparation and to their use in the preparation of various materials, in particular organic semiconductors and dyes. BACKGROUND OF THE INVENTION Dye-sensitized solar cells (DSSCs) are a promising photovoltaic technology for the production of renewable and low-cost energy. These cells consist of a nanocrystalline oxide with a large energy gap, for example TiO 2 deposited on a transparent conductive oxide glass support. Molecular sensitizers, bonded through wide-gap oxide anchoring groups, inject electrons into the conduction band of the semiconductor under solar exposure. Usually, a liquid electrolyte comprising a redox system provides regeneration of the photoexcited dye. Today, liquid electrolyte based DSSCs achieve conversion efficiencies of more than 12%. However, they can cause problems of leakage and corrosion of the electrodes. A strategy that was developed a few years ago, consists in the manufacture of "solid state" DSSC (ssDSSC) obtained by replacing the liquid electrolyte with a p-type organic semiconductor or an associated polymer matrix. to a redox couple. For this purpose various pi-conjugated compounds such as derivatives of triphenylamine, carbazole or conjugated polymers such as poly (3,4-ethylenedioxythiophene) (PEDOT) or poly-3-hexylthiophene (P3HT) have been proposed. Currently, one of the most studied materials is 2,2,7,7-tetrakis- (N, N-di-p-methoxyphenylamine) -9,9-spirobifluorene or spiro-OMeTAD which has become the reference molecule for an organic semiconductor carrier of holes. The results obtained with this type of molecular glass exceed those obtained with liquid cells, since the use of perovskite-type sensitizers which made it possible to achieve conversion efficiencies of more than 15%. Recently, the inventors have synthesized new di-substituted carbazole-based organic hole-transporting materials at positions 3 and 6 useful for the manufacture of molecular glasses (Martial Degbia et al., Carbazole-based molecular glasses for 3). , 44% efficient solid-state dye-sensitized solar cells Journal of Power Sources, 233 (2013) 86-92); Among the compounds described, 3,6-di (4,4-dimethoxydiphenylaminyl) -9-phenylcarbazole has been shown to be very promising since it gives results almost as high as the Spiro-OMeTAD conventionally used with conversion yields. of the order of 3.44% under conditions of realization of non-optimized PV devices. Although these all-solid dye devices can be easily made, thus making it possible to overcome the problems of electrolyte corrosion, leakage and temperature limitation, the processes making it possible to access these molecules, in particular to the molecule. (spiro-OMeTAD) are still very expensive. Also it is necessary to find new synthons making it easy to prepare a range of low-cost, high-performance molecular glasses, with adaptable chemical structures and having a common core suitable for producing solid DSSC with high efficiency of energy conversion. solar. However, the inventors have discovered that, from particular synthons, especially carbazole or fluorene-based synthons, which can be chemically modified in an easy manner, it is possible to prepare a wide range of amorphous, hole-carrying, good-possessing molecules. mobilities, energy levels suitable for regeneration of the photooxidized dye, and having optical and semiconductive properties suitable for use in DSSCs. The interest of these synthons is the possibility of developing many t-conjugated organic materials, in particular thanks to the reactivity of the 9-position on the carbazole or fluorene ring. The synthesis of these t-conjugated materials 3024144 -3 even if they have complex structures can be carried out in a single step from said synthons and a well-chosen connector center. These t-conjugated materials have applications in optoelectronics, especially for charge transport and / or photon absorption. By way of example, OLEDs, organic transistors and organic and hybrid photovoltaic cells may be mentioned. Thus, the purpose of the invention is to provide a process for the preparation of t-conjugated materials from new synthons. The invention also aims to provide new synthons and their manufacturing process. Also, the present invention relates to a process for synthesizing t-conjugated materials comprising a step of implementing a synthon of formula (I) in which - W represents either a group -CHR5-, or a group -N (H) -, - R1 and R2, identical or different, are respectively in position 3 and 6 or position 2 and 7 of the ring and are selected independently of each other in the group comprising 25 i. hydrogen, ii. mono or polycyclic aromatic groups, said groups possibly being substituted with at least one straight or branched C1-C12 alkyl group, in particular a methyl group, or with a straight or branched C1-C12 alkoxy group, especially a methoxy, iii . the groups Ar 2 and Ar 2, wherein Ari and Ar 2, which are identical or different, each independently represent an aryl group, optionally substituted with one or more identical or different substituents chosen; among: 10 a. the hydrogen atom, b. straight or branched C1-C12 alkyl groups, said alkyl groups being saturable or unsaturated and may comprise one or more heteroatoms selected from O and S, c. straight or branched C1-C12 alkoxy, said alkoxy groups being saturable or unsaturated and may comprise one or more heteroatoms selected from O and S, d. oligoethers and 20 e. oligothioethers, with the proviso that R 1 and R 2 are not simultaneously hydrogen, R 3 and R 4, which are identical or different, occupy the positions left free by R 1 and R 2 and are chosen from: a. hydrogen b. halogens c. the nitro group, d. the sulfonate group, e. amine groups, 30 f. carbonyl groups, g. mono or polycyclic aromatic groups h. straight or branched C1-C12 alkyl groups, said alkyl groups being saturable or unsaturated and may include one or more heteroatoms selected from O and S, i. straight or branched C1-C12 alkoxy, wherein said alkoxy groups may be saturated or unsaturated and may include one or more heteroatoms selected from O and S, j. oligoethers and k. oligothioethers. R5 is selected from: 10 a. straight or branched C1-C12 alkyl groups, said alkyl groups being able to be saturated or unsaturated and possibly containing one or more heteroatoms chosen from O and S, b. oligoethers and 15 c. oligothioethers. When W is -CR 5 -, then the synthon is a fluorene derivative of formula (Ia) (Ia) and when W is -N (H) -, then the synthon is a carbazole derivative of formula (Ib) 30 (Ib) 3024144 -6 When R1 and R2 are in position 3 and / or 6 or 2 and / or 7 of the carbazole ring, then R3 and R4 are at position 1 and 5 or 4 and 8 of said ring. For the purposes of the present invention, the mono or polycyclic aromatic groups comprise from 6 to 50 carbon atoms. Advantageously, they comprise from 6 to 18 carbon atoms and are mono-, bi- or tricyclic. When the carbocyclic group comprises more than one ring nucleus, the cyclic rings can be fused pairwise or pairwise attached by α bonds. Two fused rings may be ortho-condensed or pericondensed. The carbocyclic radical may comprise a saturated part and / or an aromatic part and / or an unsaturated part. Examples that may be mentioned include (C 6 -C 18) aryl groups and in particular phenyl, benzyl, tolyl, xylyl, naphthyl, anthryl, phenanthryl, biphenyl, terphenyl, tetrahydronaphthyl, fluorene and carbazole groups. These mono- or polycyclic, and especially mono-, bi- or tricyclic radicals may comprise one or more heteroatoms selected from O, S and / or N, preferably 1 to 4 heteroatoms. Preferably, the monocycles or the monocycle constituting the heterocycle, has from 5 to 12 ring members, more preferably from 5 to 10 ring members, for example from 5 to 6 ring members. By way of example, mention may be made of mono- or polycyclic, unsaturated or aromatic heterocycles, pyridine, furan, thiophene, pyrrole, pyrrazole, imidazole, thiazole, isoxazole, and the like. isothiazole, pyridazine, pyrimidine, pyrazine, triazines, indolizine, indole, isoindole, benzofuran, benzothiophene, indazole, benzimidazole, benzothiazole, purine, quinoline, isoquinoline, cinnoline, phthalazine, quinazoline, quinoxaline, pteridine, naphthyridines, carbazole, phenothiazine, phenoxazine, acridine, phenazine, oxazole, pyrazole, oxadiazole, triazole , thiadiazole and their unsaturated derivatives. Other examples are the unsaturated derivatives of pyrrolidine, dioxolane, imidazolidine, pyrazolidine, piperidine, dioxane, morpholine, dithiane, thiomorpholine, piperazine and trithiane. According to the invention, the term "straight-chain or branched C 1 -C 12 alkyl or (C 1 -C 12) alkyl group means said alkyl group which may be saturated or unsaturated and may comprise one or more heteroatoms chosen from O and S, a saturated or unsaturated, linear or branched chain of 1 to 15 carbons said carbon atoms may be replaced by one or more heteroatoms selected from O and S. Examples that may be mentioned include methyl, ethyl, propyl groups; isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, neopentyl, 2-methylbutyl, 1-ethylpropyl, hexyl, isohexyl, neohexyl, 1-methylpentyl, 3-methylpentyl, 1,1-dimethylbutyl, 1 3-dimethylbutyl, 2-ethylbutyl, 1-methyl-1-ethylpropyl, heptyl, 1-methylhexyl, 1-propylbutyl, 4,4-dimethylpentyl, octyl, 1-methylheptyl, 2-ethylhexyl, 5,5-dimethylhexyl, nonyl, decyl, 1-methylnonyl, 3,7-dimethyloctyl and 7,7-di methyloctyl. According to the invention, the straight or branched C1-C12 alkoxy or (C1-C12) alkoxy groups represent an alkoxy group comprising from 1 to 12 carbon atoms, said alkoxy groups being able to be saturated or unsaturated and possibly comprising a or several heteroatoms chosen from O and S. By way of example, mention may be made of methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, secbutoxy and tert-butoxy groups.
    [0002] In accordance with the invention, oligoether groups are understood to mean oligomers whose organic repeating units are held together by ether functions (C-O-C). Advantageously, the olioethers according to the invention comprise two to five ether groups and from 2 to 4 repeating units. As an example of oligoethers, mention may be made of diethylene glycol, triethylene glycol, tetraethylene glycol and pentaethylene glycol. According to the invention, the term "oligothioether group" means oligomers whose organic repeating units are held together by thioether (C-S-C) functions. Advantageously, the oliothioethers according to the invention comprise two to three thioether groups and from 2 to 4 repeating units. As an example of oligothioethers, mention may be made of ethanedithiol. According to the invention, halogen is understood to mean an atom chosen from the group comprising bromine, chlorine, fluorine and iodine.
    [0003] In accordance with the invention, the term nitro group, a group -NO2 and a sulfonate group, a group --SO2. In accordance with the invention, amine groups are understood to mean primary (-NH 2), secondary or tertiary amines.
    [0004] According to the invention, the term "carbonyl groups" means the groups = C = O, -CHO, -COR, R being a C 1 -C 12 alkyl group. By way of examples of particularly advantageous groups for R 1 and R 2, mention may be made of: ## STR1 ## in which: E = oligo-ether D = alkyl-D = alkyl E = oligo-ether 3024144 -9 In one embodiment Advantageous of the process of the invention is a compound of formula (I), wherein R1 and R2 each independently represent a group selected from: i. phenyl, naphthyl, anthracenyl, indenyl, biphenyl, terphenyl and carbazolyl groups, said groups possibly being substituted with at least one straight or branched C1-C12 alkyl group, especially a methyl group, ii. the groups Ra Ra and Ra 15 where Ra and Rb, identical or different, each represent independently of each other: a. either a hydrogen atom, b. or a straight or branched C1-C12 alkyl group, said alkyl group may be saturated or unsaturated and may include one or more heteroatoms selected from O and S, c. is a straight or branched C1-C12 alkoxy group, said alkoxy group may be saturated or unsaturated and may comprise one or more heteroatoms selected from O and 25 S, in particular a methoxy group, d. an oligoether, e. an oligothioether. In an even more advantageous embodiment of the process of the invention, compounds of formula (I) in which R 3 and R 4 each represent a hydrogen atom are used; these compounds therefore correspond to the formula (I ') in which R1 and R2 are as defined above.
    [0005] The process of the invention makes it possible to prepare a wide range of t-conjugated materials of different structure and properties, in particular compounds of formula (Ib ') (Ib') in which R1 and R2, which are identical or different, are respectively in position 3 and 6 or position 2 and 7 of the cycle and are chosen independently of one another in the group comprising i. hydrogen, ii. the aryl groups, said aryl groups possibly being substituted with at least one straight or branched C1-C5 alkyl group, especially a methyl group, iii. the groups 20 / -N Ar and AriA r2 Ar1 2 3024144 where Ari and Are, identical or different, each independently represent an aryl group, optionally substituted with one or more identical or different substituents chosen from: a. the hydrogen atom, b. straight or branched C1-C12 alkyl groups, said alkyl groups being able to be saturated or unsaturated and possibly containing one or more heteroatoms chosen from O and S, c. straight or branched C1-C12 alkoxy, said alkoxy groups being saturable or unsaturated and may comprise one or more heteroatoms selected from O and S, d. oligoethers and e. oligothioethers, with the proviso that R 1 and R 2 are not simultaneously hydrogen, - R 3 and R 4, which are identical or different, occupy the positions left free by R 1 and R 2 and are chosen from: a. hydrogen, b. halogens, c. the nitro group, d. the sulfonate group, e. amine groups, f. carbonyl groups, 25 g. mono or polycyclic aromatic groups h. straight or branched C1-C12 alkyl groups, said alkyl groups being saturable or unsaturated and possibly having one or more heteroatoms selected from O and S, i. straight or branched C1-C12 alkoxy, said alkoxy groups being saturable or unsaturated and which may comprise one or more heteroatoms selected from O and S, 3024144 - 12 - j. oligoethers and k. oligothioethers. and R 6 represents either a straight or branched C 1 -C 12 alkyl group, or a C 6 -C 18 aryl group, especially a benzene or methoxybenzene (anisole) group, or an amine protecting group, in particular a benzyl group, optionally substituted with a C1-C5 alkoxy group. The process of the invention also makes it possible to prepare t-conjugated materials having the formula (1a) or (Ib) n (Ia) (Ib) in which represents a polyfunctional central unit, i.e. function-bearing entity for grafting the carbazole ring or the fluorene ring in position 9. As examples of functions that allow grafting, mention may be made of iodine, bromine, chlorine atoms, tosylates, mesylates, etc. By way of example of polyfunctional central units, it may be noted - C6H4-, biphenylene, terphenyl, fluorenyl, carbazolyl, oligooxyethylene derivative, n is an integer equal to or greater than 2, advantageously between 2 and 6, - R1 and R2, identical or different, are respectively in position 3 and 6 or position 2 and 7 of the cycle and are chosen independently of one another in the group comprising i. hydrogen, ii. the aryl groups, said aryl groups possibly being substituted with at least one straight or branched C1-C5 alkyl group, especially a methyl group, iii. the groups Ar 1 and Ar 1, where Ar 1 and Ar 2, which are identical or different, each independently represent an aryl group, optionally substituted with one or more identical or different substituents chosen from: 25 a. the hydrogen atom, b. straight or branched C1-C12 alkyl groups, said alkyl groups being saturable or unsaturated and may comprise one or more heteroatoms selected from O and S, c. straight or branched C1-C12 alkoxy, said alkoxy groups being saturable or unsaturated and which may comprise one or more heteroatoms selected from O and S, 3024144 - 14 - d. oligoethers and e. oligothioethers, with the proviso that R1 and R2 are not simultaneously hydrogen, R3 and R4 are identical or different and occupy the positions left free by R1 and R2 and are selected from: a. hydrogen b. halogens c. the nitro group, 10 d. the sulfonate group e. amine groups, f. carbonyl groups, g. mono or polycyclic aromatic groups h. straight or branched C1-C12 alkyl groups, said alkyl groups being saturable or unsaturated and possibly having one or more heteroatoms selected from O and S, i. straight or branched C1-C12 alkoxy, wherein said alkoxy groups may be saturated or unsaturated and may include one or more heteroatoms selected from O and S, j. oligoethers and k. the oligothioethers R5 represents: a) a straight or branched C1-C12 alkyl group, said alkyl groups being saturable or unsaturated and possibly containing one or more heteroatoms selected from O and S, b) the oligoethers and c) either oligothioethers. By way of example, compounds of formula (Ia) and (Ib) may be mentioned corresponding to compounds of formula (1a) and (Ib) for which n (1a2) corresponding to compounds of formula (1a) and (1b) for which n = 3 5 10 15 20 25 (1a3) 3024144 Corresponding to compounds of formula (Ib) and (Ib ') for which n = 4. The interest of the various synthons used in the process according to the invention is the possibility of elaboration of numerous t-conjugated organic materials, in particular thanks to the reactivity of the amine function available at position 9 of the carbazole ring and that of of the function at position 9 of fluorene. The t-conjugated organic materials derived from said synthons can be polyfunctional, ie they have a center connected to several synthons. Also the process according to the invention gives a wide possibility of synthesis of new t-conjugated organic materials. In addition, the synthesis of these t-conjugated materials is made easy by the use of the synthon since one can have access to certain t-conjugated materials of complex structures in a single step from this synthon. These t-conjugated materials have applications in optoelectronics, especially for charge transport and / or photon absorption. OLEDs, organic transistors, organic and hybrid photovoltaic cells may be mentioned as examples. The compounds of formula (Ia), (Ib) and (Ib ') (la) (Ib) R 2 (Ib') in which R 1 and R 2, which are identical or different, are respectively in position 3 and 6 or position 2 and 7 of the cycle and are chosen independently of one another in the group comprising i. hydrogen, ii. halogens, iii. the aryl groups, said aryl groups possibly being substituted with at least one straight or branched C1-C5 alkyl group, especially a methyl group, iv. the groups N 1 - Ar Ar 2 and Ar 1 Al 2 where Ar 1 and Ar 2, which are identical or different, each independently represent an aryl group, optionally substituted with one or more identical or different substituents chosen from: at. the hydrogen atom, b. straight or branched C1-C12 alkyl groups, said alkyl groups being saturable or unsaturated and may include one or more heteroatoms selected from O and S, c. straight or branched C1-C12 alkoxy, said alkoxy groups being saturable or unsaturated and may comprise one or more heteroatoms selected from O and S, d. oligoethers and e. oligothioethers, with the proviso that R 1 and R 2 are not simultaneously hydrogen, R 3 and R 4, which are identical or different, occupy the positions left free by R 1 and R 2 and are chosen from: a. hydrogen, b. halogens, 3024144 - 21 - c. the nitro group, d. the sulfonate group, e. amine groups, f. carbonyl groups, 5 g. mono or polycyclic aromatic groups h. straight or branched C1-C12 alkyl groups, said alkyl groups being saturable or unsaturated and may comprise one or more heteroatoms selected from O and S, i. straight or branched C1-C12 alkoxy, said alkoxy groups being saturable or unsaturated and may comprise one or more heteroatoms selected from O and S, j. oligoethers and 15 k. the oligothioethers R5 is chosen from: a. straight or branched C1-C12 alkyl groups, said alkyl groups being saturable or unsaturated and may comprise one or more heteroatoms selected from O and S, b. oligoethers, c. the oligothioethers, R6 represents either a straight or branched C1-C12 alkyl group or a C6-C18 aryl group, especially a benzene or methoxybenzene (anisole) group, or an amine protecting group, in particular a benzyl group; optionally substituted by a C1-C5 alkoxy group are new and form part of the invention. The compound of formula: ## STR2 ## The compounds of formula (I) may be prepared by any technique known to those skilled in the art from compounds available commercially or which may be prepared according to the invention. techniques known to those skilled in the art or described in the literature. Thus the method illustrated in Scheme 1 which follows may be used: Ibl Scheme 1 The first step (ii) is the iodination of positions 3 and 6 of carbazole in acetic acid at 85 ° C in the presence of iodide of potassium and potassium iodate as described by Tucker, SHJ Chem. Soc. 1926, 129, 546. It is followed by a second step (i) which consists of a protection of the amine at the 9-position of diiodocarbazole with a benzyl group in the presence of sodium hydride in anhydrous tetrahydrofuran (THF). at room temperature (Estrada, LA, Neckers, DC Organic Letters 2011, 13, 3304). In a third step, a C-N coupling makes it possible to bind the bis (4-methoxyphenyl) amine group to the 3 and 6 positions of the carbazole unit; this step is carried out in toluene at 110 ° C in the presence of a palladium catalyst, tris-tert-butylphosphine and sodium butyloxate (Yamamoto, T. Nishiyama, M. Koie, Y. Tetrahedron Letters 1998, 39 , 2367). The last step is a deprotection reaction to remove the benzyl moiety from the 9-position of the carbazole core to make the amine function available for later use; it is carried out in THF and dimethylsulfoxide (DMSO) in the presence of potassium and oxygen terbutylate (Haddach, A. A. Kelleman, A. Deaton-Rewolinski, M. V. Tetrahedron letters 2002, 43, 399).
    [0006] The compounds of formula (I) as defined above may also be prepared by a process comprising: a) a step of protecting W when W represents a group -N (H) - in the compound of formula (II) and R3 and R4, which are identical or different, are chosen from i. hydrogen, ii. halogens, iii. the nitro group, iv. the sulfonate group, y. amine groups, vi. carbonyl groups, vii. mono or polycyclic aromatic groups, viii. straight or branched C1-C12 alkyl groups, said alkyl groups being saturable or unsaturated and may comprise one or more heteroatoms selected from O and S, ix. straight or branched C1-C12 alkoxy, wherein said alkoxy groups may be saturated or unsaturated and may include one or more heteroatoms selected from O and S, x. oligoethers and xi. oligothioethers, with the proviso that if R3 is in position 2 then R4 is not in position 7 and if R3 is in position 3 then R4 is not in position 6, to give a compound of formula ( III) wherein GP is an amine protecting group, b) treating the compound of formula (II) wherein W represents a -CHR6- group or a compound of formula (III) by a halogenated derivative, to give a compound of formula (IVa) or (IVb) (IVa) (IVb) wherein - R3 and R4 are as defined in claim 1 and 3024144 - X, in position 2 and 7 of fluorene or 3 and 6 of carbazole represents a halogen atom, especially an iodine or bromine atom, c) a coupling reaction of said compound of formula (IVb) or (IVa) to give a compound of formula (Vb) or (Ia) (la) (Vb) wherein R1, R2, R3 and R4 are as defined above and d) if necessary deprotecting the compound of formula (Vb) to give a compound of formula (Ib).
    [0007] The subject of the invention is also t-conjugated materials of formula (Ib1) 10 (Ib1) in which - R1 and R2, which are identical or different, are respectively in position 3 and position 6 or in position 2 and 7 carbazole and are independently selected from the group consisting of i. the aryl groups, said aryl groups possibly being substituted with at least one straight or branched C1-C5 alkyl group, in particular a methyl group, ii. the groups Ar 1 Ar 2 and Ar 1 Ar 2 where Ar 1 and Ar 2, which are identical or different, each independently represent an aryl group, optionally substituted with one or more identical or different substituents chosen from: a. the hydrogen atom, b. straight or branched C1-C12 alkyl groups, said alkyl groups being saturable or unsaturated and may include one or more heteroatoms selected from O and S, c. straight or branched C1-C12 alkoxy, said alkoxy groups being saturable or unsaturated and having one or more heteroatoms selected from O and S, d. oligoethers and e. oligothioethers with the proviso that R1 and R2 are not simultaneously hydrogen, R3 and R4 are the same or different and occupy the positions left free by R1 and R2 and are selected from: a. hydrogen, b. halogens, c. the nitro group, d. the sulfonate group, e. amine groups, f. carbonyl groups, g. mono or polycyclic aromatic groups, 20 h. straight or branched C1-C12 alkyl groups, said alkyl groups being saturable or unsaturated and may comprise one or more heteroatoms selected from O and S, i. straight or branched C1-C12 alkoxy, said alkoxy groups being saturable or unsaturated and may comprise one or more heteroatoms selected from O and S, j. oligoethers and k. oligothiethers and Q represents a spacer selected from the group consisting of: a. C1-C12 alkyl groups, b. arylenyl groups, 3024144 c. oligoethers and d. Oligothioethers By way of example of compound (Ib), the following compounds may be mentioned: ## STR5 ## The compounds of Formula (Ib1) can be prepared by any technique known to those skilled in the art from the synthons of the invention, using commercially available products or which can be prepared according to techniques known to those skilled in the art. or described in the literature. Thus it is possible to prepare the compounds of formula (Ib1) by reacting a synthon of formula (I) wherein W, R1, R2, R3, and R4 are as previously defined with a compound of formula Where X represents a halogen atom, especially an iodine or bromine atom to obtain a compound of formula (Ib1) 5 (Ib1) A very promising application of the present invention is the field of organic photovoltaic and particularly dye-sensitized solar cell dye cells (DSSC). The process according to the invention has already made it possible to synthesize a certain number of t-conjugated, semiconducting organic molecules whose use in place of the liquid electrolyte in DSSCs has given very promising preliminary results. The best materials used under the same conditions as the market reference molecule (spiro-OMeTAD), give comparable photovoltaic performances. These results demonstrate the strong potential of the present invention in this field since it will make it possible to develop many organic semiconductors to manufacture DSSC solid electrolyte. Moreover, the synthon may also be used to develop dyes having chemical structure similarities with semiconductors derived from this same synthon. Having strong affinities between the semiconductor and the dye will increase the dye / semiconductor interactions, which is favorable for the pore filling of the sensitized TiO 2.
    [0008] Examples 1 to 5 which follow illustrate the invention. Example 1: Synthesis of N3, N3, N6, N6, Tetrakis (4-methoxyphenyl) -9H-carbazole-3,6-diamine (brick 3.6) This is carried out according to Scheme 1. IbI 10 The first step is a protection of the amine at the 9-position of carbazole with a benzyl group according to Estrada, LA; Neckers, D.C. Organic Letters 2011, 13, 3304. The second step consists of iodination of the 3 and 6 positions of the carbazole core according to Tucker, S.H. J. Chem. Soc. 1926, 129, 546. In a third step, a C-N coupling makes it possible to bind the bis (4-methoxyphenyl) amine group to the 3 and 6 positions of the carbazole unit according to Yamamoto, T .; Nishiyama, M .; Koie, Y. Tetrahedron Letters 1998, 39, 2367. The last step is a deprotection reaction to remove the benzyl moiety from the 9-position carbazole core to make available the amine function for further use according to Haddach, A. A .; Kelleman, A .; Deaton-Rewolinski, M. V.
    [0009] Tetrahedron setters 2002, 43, 399. 1.1. Synthesis of 9-benzyl-9H-carbazole (1) In a solution of carbazole (10 mmol, 1.7 g, 1 eq) in anhydrous tetrahydrofuran (about 30 mL) at room temperature, sodium hydride (20 mmol) , 0.7g, 2 eq) is added slowly. There is a gas evolution (H2 which is released) and the solution changes from yellow to whitish. The mixture is left stirring at room temperature for one hour when the solution becomes light brown. Benzyl bromide (1.8 mL, 1.5 eq) is added dropwise to the stirred mixture at room temperature. The mixture is left stirring for about 3 hours and TLC is made to check if the reaction is complete. At the end of the reaction, water is added to the reaction mixture which is extracted with diethyl ether. The combined organic phases were dried with MgSO 4 and the solvent was then evaporated. The solid obtained is washed with n-hexane.
    [0010] The product is obtained in the form of a low-density white solid. Yield: 80% 1.2. Synthesis of 9-benzyl-3,6-diiodo-9H-carbazole (2) In a flask 9-benzyl-9H-carbazole of the step obtained in step 1.1. (16 mmol, 4.1 g, 1 eq) is dissolved in glacial acetic acid (40-50 mL) at 80 ° C. After complete dissolution of 9-benzyl-9H-carbazole, potassium iodide (KI, 20.8 mmol, 3.5 g, 1.3 eq) and potassium iodate (KI0 3, 12.8 mmol, 2 , 75g, 0.8 eq) are then added. The temperature is maintained at 80 ° C until the complete consumption of the 12 formed. The mixture is then allowed to stir at 80 ° C. until a white precipitate appears. After the appearance of the precipitate, TLCs are made to check if the reaction is complete. A solution of sodium thiosulfate at 5% is then added to the reaction mixture after returning to ambient temperature and the precipitate is recovered by filtration and then washed several times with water. The solid obtained is dried.
    [0011] The product is obtained in the form of a white solid. Yield: 98% 1.3. 9-benzyl-N3, N3, N6, N6, Tetrakis (4-methoxyphenyl) -9H-carbazole-3,6-diamine (3) In a schlenk, diphenylamine (10 mmol, 2.3 g, 1 eq), Diiodinated carbazole obtained in step 1.2. (5 mmol, 2.54 g, 0.5 eq), tristbutylphosphine (0.2 mmol, 0.1 mL, 0.2 eq) and palladium acetate (Pd (OAc) 2; 0.2 mmol, 5 mg, 0.2 eq) are added. After having adapted the bicol to a refrigerant, the mixture is placed under an argon atmosphere. Toluene (80 mL) is then added to the reagent mixture. After stirring for 15 minutes, at room temperature, sodium terbutoxylate (13 mmol, 1.25 g, 1.3 eq) is added to the reaction mixture. After adding the base, the mixture is refluxed at 110 ° C for one day. TLCs are made to check the end of the reaction. Once the reaction is complete, the crude is filtered with celite. The filtrate obtained is purified by column chromatography (eluent = petroleum ether / ethyl acetate 8: 2). The product is obtained in the form of a yellow powder. Yield: 93% 1.4. N3, N3, N6, N6, tetrakis (4-methoxyphenyl) -9H-carbazole-3,6-diamine (brick, 3.6) The benzylcarbazole derivative obtained in step 1.3. (2 mmol, 1.45 g, 1 eq) is added to a flask and the medium is then placed under an argon atmosphere. Dimethylsulfoxide (DMSO) is then added and the reaction mixture is stirred at room temperature. A solution of potassium tert-butoxide (KOtBu) at 1M in THF (12 mmol, 1.4 g, 6 eq, ie 12 mL of a solution of KOtBu at 1M in THF) is then added to the mixture. The argon inlet is stopped and oxygen is bubbled into the reaction medium, which remains stirred at ambient temperature for approximately 3 hours. TLCs are made to see the progress of the reaction. At the end of the reaction, water is added to the mixture and the crude is extracted with acetate. The organic phase is washed with saturated NaHCO 3 solution to remove the formed benzoic acid and then with salt water. The organic phase is then dried with MgSO 4 and the solvent is evaporated. After purification by chromatographic column (eluent = petroleum ether / ethyl acetate 7: 3), the product is obtained in the form of a light yellow powder. Yield: 80% Example 2: Synthesis of 9,9 '- (1,4-phenylene) bis (N3, N3, N6, N6, tetrakis (4-methoxyphenyl) -9H-carbazole-3,6- diamine) In a microwave reaction tube were added N3, N3, N6, N6, tetrakis (4-methoxyphenyl) -9H-carbazole-3,6-diamin (brick 3.6) prepared at room temperature. Example 1 (0.48 mmol, 300 mg, 1 eq), 4,4'-diiodophenyl (0.24 mmol, 81 mg, 0.5 eq), potassium carbonate (K 2 CO 3, 3.84 mmol, 540 mmol). mg, 8 eq), copper (1.92 mmol, 120 mg, 4 eq) and 18-crown-6 ether (0.03 mmol, 10 mg, 0.06 eq). After having placed the tube containing the reagents under an inert atmosphere, 3 to 5 ml of orthodichlorobenzene are added thereto. The reaction medium is heated by microwave at 210 ° C. for approximately 1 hour. TLCs are performed to see the progress of the reaction and at the end of the reaction, the reaction mixture is filtered to remove the remainder of the inorganic reagents. The filtrate obtained is concentrated in the evaporator (by evaporating a part of orthodichlorobenzene). The crude obtained is purified by precipitation in acetone to obtain a pale green solid.
    [0012] Yield: 50% Example 3: Synthesis of 9,9 '- ([1,1'-biphenyl] -4,4'-diyl) bis (N3, N3, N6, N6, Tetrakis (4) -methoxyphenyl) -9H-carbazole-3,6-diamine) o--0 0 po N eeq NO 6 N 0 10 In a microwave reaction tube was added the brick [3,6] prepared in the example 1 (0.48 mmol, 300 mg, 1 eq), 4,4'-diiodobiphenyl (0.24 mmol, 98 mg, 0.5 eq), potassium carbonate (K 2 CO 3, 3.84 mmol, 540 mg, 8 eq), copper (1.92 mmol, 120 mg, 4 eq) and 18-crown-6 ether (0.03 mmol, 10 mg, 0.06 eq) are added. After having placed the tube containing the reagents under an inert atmosphere, 3 to 5 ml of ortho-dichlorobenzene are added thereto. The reaction medium is heated by microwave at 210 ° C. for approximately 1 hour. TLCs were performed to see the progress of the reaction. At the end of the reaction, the reaction mixture is filtered to remove the remainder of the inorganic reagents. The filtrate obtained was concentrated in the evaporator (by evaporating a part of orthodichlorobenzene). The crude obtained is purified by precipitation in acetone to obtain a pale green solid. Yield: 43% Example 4: Synthesis of 9,9 '- (9,9-dihexy-9H-fluorene-2,7-diyl) bis (N3, N3, N6, N6, tetrakis (4-methoxyphenyl) -9H -carbazole-3,6-diamine) 4.1. Synthesis of 9,9'-dihexyl-2,7-diiodo-9H-fluorene 4.1.1. Synthesis of 2,7-diiodo-9H-fluorene Fluorene (4 g, 24 mmol, 1 eq) is dissolved in a mixture containing acetic acid (60 ml), water (13 ml) and sulfuric acid (2 mL) at 95 ° C. After reducing the temperature to 80 ° C., the diiodine (4.2 g, 16.6 mmol, 0.7 eq) and the periodic acid (1.85, 8 mmol, 0.33 eq) are then added to the mixture. reaction which is then left stirring for about 1h. TLCs were performed to follow the evolution of the reaction. The precipitate formed was recovered by filtration and then washed with a saturated solution of NaHCO 3 and water. The crude solid obtained was recrystallized from n-hexane. The product is obtained in the form of a white solid. Yield: 50% 15 4.1.2. Synthesis of 9,9'-dihexy-2,2,7-diiodo-9H-fluorene In a flask, the diiodinated fluorene obtained in the preceding step, (4.2 g, 10 mmol, 1 eq), n-bromo-hexane ( 3.63 g, 22 mmol, 2.2 eq) and potassium tert-butoxide (3.36 g, 30 mmol, 3 eq) are dissolved in anhydrous THF (30 mL). After placing the medium in an inert atmosphere under argon, the reaction mixture is heated to 40 ° C and then stirred overnight. TLCs were performed to follow the evolution of the reaction. At the end of the reaction, the reaction mixture is allowed to return to room temperature and then poured into cold water. The resulting crude was extracted with diethyl ether, the combined organic phases were washed with brine and dried with MgSO 4. After evaporation of the solvent, the crude was purified by chromatographic column with eluent petroleum ether / ethyl acetate (9.5: 0.5). The product is obtained in the form of a white solid.
    [0013] Yield: 78% 4.2. Synthesis of 9,9 '- (9,9-dihexyl-9H-fluorene-2,7-diyl) bis (N3, N3, N6, N6, tetrakis (4-methoxyphenyl) -9H-carbazole-3,6-diamine In a microwave reaction tube was added the brick [3,6] prepared in Example 1 (0.48 mmol, 300 mg, 1 eq), the diiodinated derivative of the fluorene prepared at the same time. previous step (0.24 mmol, 141 mg, 0.5 eq), potassium carbonate (3.84 mmol, 540 mg, 8 eq), copper (1.92 mmol, 120 mg, 4 eq) and 18-crown-6 ether (0.03 mmol, 10 mg, 0.06 eq) are added. After having placed the tube containing the reagents under an inert atmosphere, 3 to 5 ml of ortho-dichlorobenzene are added thereto. The reaction medium is heated by microwave at 210 ° C. for approximately 2 hours. TLCs were performed to see the progress of the reaction. At the end of the reaction, the reaction mixture is filtered to remove the remainder of the inorganic reagents. The filtrate obtained was concentrated in the evaporator (by evaporating a portion of ortho-dichlorobenzene). The crude product obtained is purified by chromatographic column using the eluent: petroleum ether / ethyl acetate 7: 3.
    [0014] The product is obtained in the form of a light yellow powder. Yield: 44%. EXAMPLE 5 Synthesis of 9,9 '- ((((((oxybis (ethane-2,1-diyl) bis (oxy)) bis ( ethane-2,1-diyl) bis (4,1-phenylene) bis (N3, N3, N6, N6, tetrakis (4-methoxyphenyl) -9H-carbazole-3,6-diamine) 0- ## STR2 ## Synthesis of 4,4 '- (((((oxybis (ethane-2,1-diol), n-O-N-O-O-N-O-N-O-N-O-O Bis (oxy) bis (ethane-2,1-diyl) bis (oxy) bis (iodobenzene) 5.1.1 Synthesis of ((oxybis (ethane-2,1-diyl)) bis (oxy) )) bis (ethane-2,1-diyl)) bis (4-methylbenzenesulfonate) or ethylene glycol ditosylate In a flask, ether glycol (10 mmol, 1 eq) is dissolved in tetrahydrofuran (20 mL), tosyl chloride (25 mmol, 2.5 eq) is then added and an aqueous solution of potassium hydroxide (4m1, 16M, 64 mmol, 6.4 eq) is then added dropwise. drop to the reaction mixture. After stirring for about 7 hours at room temperature, TLCs were performed to follow the evolution of the reaction.
    [0015] At the end of the reaction, the reaction mixture is poured into a cold water solution and the precipitate formed is recovered by filtration. The product is obtained in the form of a white solid. Yield: 85% 5.1.2. Synthesis of 4,4 '- (((((oxybis (ethane-2,1-diyl) bis (oxy)) bis (ethane (2,1-diyl)) bis (oxy)) bis (iodobenzene) In a flask iodophenol (3.8 g, 17 mmol, 1 eq) is dissolved in dimethylformamide (60 ml), potassium terbutylate (2.9 g, 26 mmol, 1.5 eq) is then gently added. The ditersylate derived from the ether glycol obtained in the previous step (4.3 g, 8.5 mmol, 0.5 eq) is then added to the reaction mixture, which is left stirring overnight at room temperature. During the addition of the ditosylate, the formation of a white precipitate is observed. TLCs were performed to check the progress of the reaction. At the end of the reaction, water is added to the reaction mixture. The crude obtained is then extracted with ethyl acetate and the combined organic phases are washed with saturated NaHCO 3 solution and dried with MgSO 4. The product is obtained in the form of a white solid. Yield: 95% 5.2. Synthesis of 9,9 '- ((((((oxybis (ethane-2,1-diyl)) bis (oxy) bis (ethane-2,1-diyl) bis (4,1-phenylene) bis (N3, N3, N6, N6, tetrakis (4-methoxyphenyl) -9H-carbazole-3,6-diamine) In a microwave reaction tube was added the brick [3,6] prepared according to the example 1 (0.48 mmol, 300 mg, 1 eq), the diiodinated derivative of ethylene glycol prepared in the previous step (0.24 mmol, 98 mg, 0.5 eq), potassium carbonate (3, 84 mmol, 540 mg, 8 eq), copper (1.92 mmol, 120 mg, 4 eq) and 18-crown-6 ether (0.03 mmol, 10 mg, 0.06 eq) are added. After having placed the tube containing the reagents under an inert atmosphere, 3 to 5 ml of ortho-dichlorobenzene are added thereto, The reaction medium is heated by microwave at 210 ° C. for about 1 hour. In order to see the progress of the reaction, at the end of the reaction, the reaction mixture is filtered to remove the remainder of the inorganic reactants. ty concentrated in the evaporator (5 evaporating a portion of ortho-dichlorobenzene). The crude product obtained is purified by chromatographic column using the eluent: petroleum ether / ethyl acetate 7: 3. The product is obtained in the form of a green-colored powder. Yield: 45%
    权利要求:
    Claims (9)
    [0001]
    REVENDICATIONS1. A process for synthesizing t-conjugated materials comprising a step of implementing a synthon of formula (I) (I) in which - W represents either a -C (HR5) - group or a -N (H) group -, - R1 and R2, identical or different, are respectively in position 3 and 6 or position 2 and 7 of the cycle and are chosen independently of one another in the group comprising i. hydrogen, ii. the mono or polycyclic aromatic groups, said groups possibly being substituted with at least one straight or branched C1-C12 alkyl group, especially a methyl group, or with a straight or branched C1-C12 alkoxy group, especially a methoxy, iii. the groups / ArN and A A r2 Ari 2 where Ar1 and Ar2, which are identical or different, represent each independently of each other an aryl group, optionally substituted with one or more identical or different substituents chosen from: ## STR2 ## the hydrogen atom, b. straight or branched C1-C12 alkyl groups, said alkyl groups being saturable or unsaturated and may comprise one or more heteroatoms selected from O and S, c. straight or branched C1-C12 alkoxy, said alkoxy groups being saturable or unsaturated and may comprise one or more heteroatoms selected from O and S, and d. the oligoethers provided that R1 and R2 are not simultaneously hydrogen, R3 and R4 identical or different occupy the positions left free by R1 and R2 and are selected from: a. hydrogen b. halogens c. the nitro group, d. the sulfonate group, e. amine groups, 20 f. carbonyl groups, g. mono or polycyclic aromatic groups h. straight or branched C1-C12 alkyl groups, said alkyl groups being saturable or unsaturated and may comprise one or more heteroatoms selected from O and S, i. straight or branched C1-C12 alkoxy, said alkoxy groups being saturable or unsaturated and may comprise one or more heteroatoms selected from O and S, and 30 j. the oligoethers R5 is chosen from: d. straight or branched C1-C12 alkyl groups, said alkyl groups being saturable or unsaturated and may include one or more heteroatoms selected from O and S, e. (C6-C18) aryl groups, f. oligoethers, 5 g. oligothioethers, h. heterocycles and i. heteroaryls.
    [0002]
    2. Method according to claim 1, characterized in that in the compound of formula (I), R1 and R2 each independently represent a group chosen from: L phenyl, naphthyl, anthracenyl, indenyl, biphenyl, terphenyl, carbazolyl, said groups may be substituted by at least one straight or branched C 1 -C 12 alkyl group, especially a methyl group, ii. the groups Rb and where Ra and Rb, identical or different, each represent independently of each other: a. either a hydrogen atom, b. is a straight or branched C1-C12 alkyl group, said alkyl group may be saturated or unsaturated and may comprise one or more heteroatoms selected from O and S, c. is a straight or branched C1-C12 alkoxy group, said alkoxy group may be saturated or unsaturated and may comprise one or more heteroatoms selected from O and S, in particular a methoxy group, d. an oligoether, e. an oligothioether.
    [0003]
    3. Method according to any one of the preceding claims characterized in that in the compound of formula (I), R3 and R4 10 each represent a hydrogen atom.
    [0004]
    4. Method according to any one of the preceding claims, characterized in that the t-conjugated materials correspond to the formula (Ib ') 15 (Ib') 25 in which R1 and R2, identical or different, are respectively in position 3 and 6 or in position 2 and 7 of the cycle and are selected independently of each other in the group consisting of 30 i. hydrogen, ii. the aryl groups, said aryl groups possibly being substituted with at least one linear or branched C1-C12 alkyl group, especially a group iii. the groups Ar 2 Ar 2 Ar 2 and Ar 1 wherein Ar 1 and Ar 2, which are identical or different, each independently represent an aryl group, optionally substituted with one or more identical or different substituents chosen from: a. the hydrogen atom, b. straight or branched C1-C12 alkyl groups, said alkyl groups being saturable or unsaturated and may comprise one or more heteroatoms selected from O and S, c. straight or branched C1-C12 alkoxy, wherein said alkoxy groups may be saturated or unsaturated and may include one or more heteroatoms selected from O and S, d. oligoethers and e. the oligothioethers with the proviso that R1 and R2 are not simultaneously hydrogen, - R3 and R4 identical or different occupy the positions left free by R1 and R2 and are selected from: a. hydrogen b. halogens c. the nitro group, d. the sulfonate group, e. amine groups, f. carbonyl groups, 3024144-g. mono or polycyclic aromatic groups h. straight or branched C1-C12 alkyl groups, said alkyl groups being saturable or unsaturated and may comprise one or more heteroatoms selected from O and S, i. straight or branched C1-C12 alkoxy, said alkoxy groups being saturable or unsaturated and may comprise one or more heteroatoms selected from O and S, f. oligoethers and g. oligothioethers and R5 is selected from: a. straight or branched C1-C12 alkyl groups, said alkyl groups being saturable or unsaturated and may comprise one or more heteroatoms selected from O and S, b. oligoethers and c. oligothioethers. 20
    [0005]
    5. Method according to any one of the preceding claims, characterized in that the t-conjugated materials correspond to the formula (1a) or (Ib) n (la) (1b) in which represents a polyfunctional central unit, that is to say, an entity carrying functions allowing the grafting in the 9-position of the carbazole ring or the fluorene ring. I - n is an integer equal to or greater than 2, advantageously between 2 and 5, - R1 and R2, identical or different, are respectively in position 3 and 6 or in position 2 and 7 of the ring and are independently selected one of the other in the group comprising i. hydrogen, ii. the aryl groups, said aryl groups possibly being substituted with at least one straight or branched C1-C5 alkyl group, especially a methyl group, iii. the groups Ar 2 Ar 2 and Ar 1 Ar 2 wherein Ar 1 and Ar 2, which are identical or different, each independently represent an aryl group, optionally substituted with one or more identical or different substituents chosen from: at. the hydrogen atom, b. straight or branched C1-C12 alkyl groups, said alkyl groups being able to be saturated or unsaturated and possibly containing one or more heteroatoms chosen from O and S, c. straight or branched C1-C12 alkoxy, said alkoxy groups being saturable or unsaturated and may comprise one or more heteroatoms selected from O and S, d. oligoethers and e. oligothioethers, with the proviso that R 1 and R 2 are not simultaneously hydrogen, R 3 and R 4, which are identical or different, occupy the positions left free by R 1 and R 2 and are chosen from: a. hydrogen b. halogens c. the nitro group, d. the sulfonate group e. amine groups, f. carbonyl groups, 30 g. mono or polycyclic aromatic groups h. straight or branched C1-C12 alkyl groups, said alkyl groups being saturable or unsaturated and may include one or more heteroatoms selected from O and S, i. straight or branched C1-C12 alkoxy, wherein said alkoxy groups may be saturated or unsaturated and may include one or more heteroatoms selected from O and S, j. oligoethers and k. Oligothioethers I. Oligothioethers R5 is selected from: a. straight or branched C1-C12 alkyl groups, said alkyl groups being saturable or unsaturated and possibly having one or more heteroatoms selected from O and S, b. oligoethers and c. oligothioethers.
    [0006]
    6. Compounds of formula (Ia), (Ib) and and (Ib ') ## STR1 ## wherein R 1 and R 2, R 2 and R 2 are identical or different, are respectively in position 3 and 6 or position 2 and 7 of the cycle and are chosen independently of one another in the group comprising i. hydrogen, ii. halogens, iii. the aryl groups, said aryl groups possibly being substituted with at least one straight or branched C1-C5 alkyl group, especially a methyl group, iv. the groups N 1 and Ar 1 Ar 2 Ar 1, Ar 2, where Ar 1 and Ar 2, which are identical or different, each represent, independently of one another, an aryl group, optionally substituted with one or more identical or different substituents chosen from: the hydrogen atom, b. straight or branched C1-C12 alkyl groups, said alkyl groups being saturable or unsaturated and may comprise one or more heteroatoms selected from O and S, c. straight or branched C1-C12 alkoxy, said alkoxy groups being saturable or unsaturated and may comprise one or more heteroatoms selected from O and S, d. oligoethers and 30 e. oligothioethers, with the proviso that R 1 and R 2 are not simultaneously a hydrogen atom, R 3 and R 4, which are identical or different, occupy the positions left free by R 1 and R 2 and are chosen from: a. hydrogen, b. halogens, 5 c. the nitro group, d. the sulfonate group, e. amine groups, f. carbonyl groups, g. mono or polycyclic aromatic groups 10 h. straight or branched C1-C12 alkyl groups, said alkyl groups being saturable or unsaturated and may comprise one or more heteroatoms selected from O and S, i. straight or branched C1-C12 alkoxy, said alkoxy groups being saturable or unsaturated and may comprise one or more heteroatoms selected from O and S, j. oligoethers and k. oligothioethers, R5 is selected from: a. straight or branched C1-C12 alkyl groups, said alkyl groups being saturable or unsaturated and may comprise one or more heteroatoms selected from O and S, b. oligoethers and c. the oligothioethers and - R6 represents either a straight or branched C1-C12 alkyl group or a C6-C18 aryl group, especially a benzene or methoxybenzene (anisole) group, or an amine protecting group, in particular a group benzyl, optionally substituted by a C1-05 alkoxy group. 3024144 - 53 -
    [0007]
    7. Process for the preparation of the compounds of formula (I) according to claim 1, characterized in that it comprises: a) a step of protecting W when W represents a group -N (H) - in the compound of formula ( II) and R3 and R4, which are identical or different, are chosen from i. hydrogen, ii. halogens, iii. the nitro group, iv. the sulfonate group, y. amine groups, vi. carbonyl groups, vii. mono or polycyclic aromatic groups, viii. straight or branched C1-C12 alkyl groups, said alkyl groups being able to be saturated or unsaturated and possibly containing one or more heteroatoms chosen from O and S, ix. straight or branched C1-C12 alkoxy, said alkoxy groups being saturable or unsaturated and may comprise one or more heteroatoms selected from O and S, x. oligoethers and xi. oligothioethers, with the proviso that if R3 is in position 2 then R4 is not in position 7 and if R3 is in position 3 then R4 is not in position 6 to give a compound of formula (III) 3024144 Wherein GP is an amine protecting group, b) treating the compound of formula (II) wherein W is -CHR5- or a compound of formula (III) with a halogenated derivative, for give a compound of formula (IVa) or (IVb) (IVa) (IVb) in which - R3 and R4 are as defined in claim 1 and - X, in position 2 and 7 of fluorene or 3 and 6 of carbazole represents a halogen atom, especially an iodine or bromine atom, c) a coupling reaction of said compound of formula (IVa) or (IVb) to give a compound of formula (Vb) or (Ia) 3024144 - Wherein R 1, R 2, R 3 and R 4 are as defined in claim 1 and d) if necessary deprotecting the compound of formula (Va) to give a compound of formula (V); ormule (Ia).
    [0008]
    8. T-conjugated materials of formula (Ib1) 10 (Ib1) in which R1 and R2, identical or different, are respectively in position 3 and 6 or in position 2 and 7 of carbazole and are independently selected one from the other in the group comprising 25 i. the aryl groups, said aryl groups possibly being substituted by at least one straight or branched C1-C4 alkyl group, especially a methyl group, ## STR2 ## the groups Ar2 and Arl Arles wherein Ar1 and Ar2, which are identical or different, each independently represent an aryl group, optionally substituted by one or more identical or different substituents chosen from: a. the hydrogen atom, b. straight or branched C1-C12 alkyl groups, said alkyl groups being saturable or unsaturated and may comprise one or more heteroatoms selected from O and S, c. straight or branched C1-C12 alkoxy, wherein said alkoxy groups may be saturated or unsaturated and may include one or more heteroatoms selected from O and S and d. the oligoethers, provided that R 1 and R 2 are not simultaneously hydrogen, R 3 and R 4, which are identical or different, occupy the positions left free by R 1 and R 2 and are chosen from: a. hydrogen, b. halogens, c. the nitro group, 30 d. the sulfonate group, e. amine groups, f. carbonyl groups, g. aromatic mono or polycyclic groups, 3024144 -57- h. straight or branched C1-C12 alkyl groups, said alkyl groups being saturable or unsaturated and may comprise one or more heteroatoms selected from O and S, i. straight or branched C1-C12 alkoxy, said alkoxy groups being saturable or unsaturated and may comprise one or more heteroatoms selected from O and S, and j. oligoethers, and Q represents a spacer selected from the group consisting of: e. C1-C12 alkylenyl groups, f. arylenyl groups, g. oligoethers and 15 h. oligothioethers
    [0009]
    9. Process for the preparation of compounds of formula (Ib1), characterized in that a synthon of formula (I) in which W, R1, R2, R3 and R4 are as defined in formula (I) is reacted. Claim 1 with a compound of formula XQX wherein X represents a halogen atom, especially an iodine atom to obtain a compound of formula (Ib1) (ibi)
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    优先权:
    申请号 | 申请日 | 专利标题
    FR1457308A|FR3024144B1|2014-07-28|2014-07-28|NOVEL SYNTHONS FOR THE PRODUCTION OF ORGANIC SEMICONDUCTORS|FR1457308A| FR3024144B1|2014-07-28|2014-07-28|NOVEL SYNTHONS FOR THE PRODUCTION OF ORGANIC SEMICONDUCTORS|
    EP15749754.6A| EP3174850A1|2014-07-28|2015-07-28|Novel synthons for developing organic semiconductors|
    JP2017505229A| JP2017523196A|2014-07-28|2015-07-28|New synthons for organic semiconductor development|
    KR1020177005744A| KR20170040301A|2014-07-28|2015-07-28|Novel synthons for developing organic semiconductors|
    PCT/EP2015/067232| WO2016016221A1|2014-07-28|2015-07-28|Novel synthons for developing organic semiconductors|
    US15/329,731| US10403445B2|2014-07-28|2015-07-28|Synthons for developing organic semiconductors|
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