FR2911875A1 - New thiacalix(2)thianthrenes e.g. useful for the extraction, trapping or recognition of molecules - Google Patents

Abstract

Thiacalix[2]thianthrenes (I) are new. Thiacalix[2]thianthrenes of formula (I) are new. X 1-X 6S, SO or SO 2; a-d : 1-3; R 1-R 4H, halo, 1-6C alkyl, phenyl, optionally substituted phenylazo, N = CHR 5, CCR 6, NO 2, NHR 7, COR 9, Si(R 10) 3or CR 11= CR 12R 13; R 51-4C alkyl, pyridyl or phenyl; R 6H, 1-4C alkyl, tri(1-4C alkyl)silyl or phenyl; R 7H or COR 8; R 81-4C alkyl, pyridyl, phenyl or halo; R 9H, halo, OH, 1-4C alkyl, aryl or alkoxy; R 10H, 1-4C alkyl or aryl; R 11-R 13H, halo, 1-4C alkyl, aryl or alkoxy. Independent claims are also included for: (1) radical cations derived from (I); (2) metal complexes of (I). [Image].

Description

The present invention relates to a new family of chemical compounds.

  The family of thiacalixarenes is a chemical family, which has already been studied by the inventors, which has nonlinear optical properties. The thianthrene family is also a family that has different potential applications in the field of pharmacy, agriculture, and as a material, for example electroluminescent property, drivers ... The inventors had the idea to develop a new family of chemical compounds that would combine the structures of these two families of compounds. In this context, the inventors propose to provide a family of compounds that combine, among others, the following properties: excellent thermal stability, improved electronic conjugation and delocalization, the presence of a cavity of suitable shape for trapping molecules.

  The subject of the present invention is therefore the compounds of formula (I): x (I) in which: X1, X2, X3, X4, X5 and X6, which are identical or different, each independently represent a sulfur atom, 0) - or -SO2-, -ni, n2, n3 and n4, identical or different, are each equal to 1, 2 or 3, - R1r R2, R3 and R4, identical or different, each independently represent: - an atom hydrogen, - a halogen atom, - a (C 1 -C 6) alkyl, phenyl group, - an optionally substituted phenylazo group, preferably in position 4 with a nitro group, - a group -N = CHR 5 in which R5 is (C1-C4) alkyl, pyridyl or phenyl; -C = C-R6 wherein R6 is hydrogen, (C1-C4) alkyl, tri (C1-C4) alkylsilyl or phenyl, a nitro group, a group -NHR7, wherein R7 represents a hydrogen atom or a -C (O) R8 group with R9 selected from a (C1-C4) alkyl, pyridyl, phenyl and halogen atoms e - a group -C (O) R 9 with R 9 which represents a hydrogen or halogen atom or a group -OH, (C 1 -C 4) alkyl, aryl, or O-alkyl, - a group Si (Rio ) With R 10 which represents a hydrogen atom or a (C 1 -C 4) alkyl or aryl group, - a group -C (R 1) = C (R 12) (R 13) with R 11, R 12, R 13 identical or different, represent, each independently, a hydrogen or halogen atom or a (C 1 -C 4) alkyl, aryl or O-alkyl group, as well as their salts, solvates and hydrates. Alkyl means a monovalent hydrocarbon radical, linear or branched, saturated, containing, unless otherwise specified, from 1 to 10 carbon atoms, preferably from 1 to 4 carbon atoms. by way of example, mention may be made of methyl, ethyl, propyl, n-butyl, tert-butyl, n-pentyl and n-hexyl groups. By (Ci-C4) alkyl is meant an alkyl radical comprising from 1 to 4 carbon atoms. By halogen atom is meant a chlorine, bromine, iodine or fluorine atom. By aryl group is meant a mono-, lai or polycyclic carbocycle comprising at least one aromatic group. Aryl groups having from 6 to 12 carbon atoms are preferred. As the aryl, mention may be made of phenyl, 1-naphthyl, 2-naphthyl, indanyl, indenyl, biphenyl and bicyclo [4.2.0] octa-1,3,5-triene, phenyl groups being preferred. The alkyl or aryl groups as defined above may be unsubstituted or substituted by one or more groups, especially chosen from halogens, nitrooxocarboxy, cyano, alkyl, trifluoroalkyl, alkenyl, alkynyl, cycloalkyl, aryl, heterocycloalkyl, amino alkylamino, dialkylamino, hydroxy, O-alkyl, O-aryl.

  The term alkenyl corresponds to an alkyl group as defined above comprising at least one double bond. Examples of alkenyl groups are, for example, vinyl, allyl, isopropenyl, 1-, 2- or 3-butenyl, pentenyl and hexenyl groups. The term alkynyl is an alkyl group as defined above comprising at least one triple bond. The term cycloalkyl denotes a cycloalkyl group comprising from 3 to 10 carbon atoms, for example cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, bridged cycloalkyl groups such as adamantyl, bicyclo [3.2.1] optanyl groups.

  The term heterocycloalkyl means cycloalkyl as defined above, comprising one or more heteroatoms selected from nitrogen, oxygen and sulfur. For the sake of simplicity, substitution of phenyl groups has been indicated (R1) n1, (R2) n2, (R3) n3, (R4) n4, respectively, but this notation does not exclude that the same phenyl group is substituted. by several different groups. Among the compounds of formula (I), the following compounds are preferred: compounds of formula (I) in which at least one of the bridges chosen from XI, X2, X3 and X4, is a sulfur atom; formula (Ia): (Ia) wherein X5, X6, R1, R2, R3 and R4, n1, n2, n3 and n4 are as defined for the compounds of formula (I), preferably X5 = X6 = S, 20 - the compounds of formula (Ib): (Ib) wherein X3, X4, X5, X6, R1, R2, R3 and R4, n1, n2, n3 and n4 are as defined for the compounds of formula ( I), - the compounds of formula (Ic): (Ic) in which X1, X2, X5, X6, R1, R2, R3 and R4, n1, n2, n3 and n4 are as defined for compounds of formula (I); I), - the compounds of formula (Id): (Id) in which X1, X2, X3, X4, R1, R2, R3 and R4, n1, n2, n3 and n4 are as defined for the compounds of formula ( I), preferably X1 = X3 = -S (O) - and X2 = X4 = S or X1 = X2 = X4 = S and X3 = -S (O) -, 410 - the compounds of formula (Ie ) : (Ie) wherein X1r X4, X5, X6, R1, R2, R3 and R4, n1, n2, n3 and n4 are as defined for compounds of formula (I), preferably X1 = X4 = X5 = X6 = SO2, Compounds of formula (If): (If) in which X1, X2, X3, X4, R1, R2, R3 and R4, n1, n2, n3 and n4 are as defined for the compounds of formula (I) the compounds of formulas (Ig): embedded image wherein X 5, X 6, R 1, R 2, R 3 and R 4, n 1, n 2, n 3 and n 4 are as defined for the compounds of formula (I) ). According to preferred embodiments, the subject of the invention is the compounds of formula (I), (Ia), (Ib), (Ic), (Id), (Ie), (If) and (Ig) which have one or more of the following characteristics when they do not exclude each other: R1 = R2 = R3 = R4,5 n1 = n2 = n3 = n4 = 1 and preferably R1, R2, R3 and R4 substitute the para position of phenyl, as illustrated below in the case of compounds of formula (Ia): - R1, R2, R3 and R4, are identical and represent a hydrogen atom, a tert-butyl group or a trimethylsilyl group. It is possible to form a radical of a compound of formula (I) by exchange of an electron at a sulfur bridge located at X1, X2, X3 or X4. In the case of the compounds of formula (I) in which X 1 = X 2 = X 3 = X 4 = S, it is possible to form on each of these sulfur bridges a radical by exchange of 1 electron and thus to obtain a radical in which at minus X1, X2, X3 or X4 is in radical form ûS + '- or a radical in which at least two of the bridges X1, X2, X3 and X4 are in radical form ûS +' -, or a radical in which at least three of the bridges. X1i X2, X3 and X4 are in radical form ûS + '-, or a radical in which all the bridges X1, X2, X3 and X4 are in radical form ûS +' -. The compounds of formula (Ia) to (Ig) have the ability to form cationic radicals by exchange of 1, 2, 3 or 4 electrons, where possible. The cationic radicals of the compounds (I) and (Ia) to (Ig) form an integral part of the invention. In the case of the compounds of formula (Ia), these radicals in particular correspond to the formula (IIa): in which X5, X6, R1, R2, R3 and R4, n1, n2, n3 and n4 are as defined for the compounds of formula (I) and 1, 2, 3 or 4 of the bridges X'1, X'2, X'3 and X'4 represent (s) a radical the others representing a sulfur atom. Such radicals can be obtained simply by oxidation reaction electrochemically, this reaction being reversible. Depending on the electrochemical potential applied, it is possible to increase the number of radicals ûS + '- obtained at the bridges X1r X2, X3 and X4 initially representing a sulfur atom. The radicals obtained can be stabilized with an anion. The subject of the present invention is also the complexes (III) of the compounds of formula (I), (Ia), (Ib), (Ic), (Id), (Ie), (If) and (Ig) and radicals compounds of formula (I), (Ia), (Ib), (Ic), (Id), (Ie), (If) and (Ig) with a metal, in particular an alkali metal, a transition metal, a lanthanide or actinide. Any type of alkali metal, transition metal, lanthanide and actinide present in Mendeleev's periodic table, as of October 2006, may be used. The metal may be in the complexes according to the invention, at various degrees of oxidation or in the form of salts. As an alkali metal, there may be mentioned, for example, cesium. As a transition metal, mention may be made, for example, of titanium, iron, copper, palladium, mercury and gold, and more preferentially silver, zinc or platinum.

  These complexes (III) are obtained according to techniques well known to those skilled in the art, for example, by adding a metal salt, for example a metal chloride, thiacalix [2] thiantrene according to the invention in solution in a suitable organic solvent, for example, tetrahydrofuran, chloroform or pyridine.

  The synthesis of the various compounds according to the invention is detailed below. The compounds of formula (I) in which R1, R2, R3 and R4, preferably in the para position, represent a hydrogen atom, a (C1-C6) alkyl group, for example tert-butyl, or a phenyl and X1 = X2 = X3 = X4 = X5 = X6 = S may be prepared by high temperature thermal treatment without solvent at a high temperature leading to cyclization, an S-thiacarbamoyl thiacalixarene of formula (IV), for example at a temperature included in the ranging from 290 to 420 C and for 0.1 to 24 hours, according to DIAGRAM 1 below.

  Wherein R1, R2, R3 and R4, preferably in the para position, each independently represent a hydrogen atom, a (C1-C6) alkyl group, for example tert-butyl, or a phenyl. R2 R3 R4 R R2 R3 R4 t. * $ S 0 S / s

  ## EQU1 ## where X1 = X2 = X3 = X4 = X5 = X6 ## EQU1 ## where X1 = X2 = X3 = X4 = X5 = X6 In Scheme 1, compounds (VI), (V) and (IV) are presented in a cone-like conformation. In fact, the compounds of formula (V) and (IV) are in the form of a mixture of alternating forms 1,2 and 1,3. The thiacalbamoyl thiacalixarene of formula (IV) is obtained by thermal rearrangement of the corresponding O-thiacarbamoyl thiacalixarene of formula (V), for example, at a temperature in the range of 270 to 300 ° C and for 2 to 4 hours, as described by Hossein 'and a /. in Journal of Supramolecular Chemistry, 2002, 2, 21. The thiacalixarenes of formula (VI) are obtained according to techniques well known to those skilled in the art, as for example described in the patent application WO 02068521. The preparation of the Compounds of formula (I) illustrated in FIG. 1 being made in the solid state, in the absence of solvent, it is easily transferable on an industrial scale.

  The compounds of formula (I) in which X1 = X2 = X3 = X4 = X5 = X6 = S and R1, R2, R3 and R4 are different from a hydrogen atom, a (C1-C6) group alkyl or phenyl, are obtained by functionalization of phenyl groups, for example by known methods for the functionalization of thiacalixarenes or thianthrenes. Reference can be made in particular to the patent application WO02068521 which describes some of these methods. These compounds can also be obtained from compounds (I) in which R1, R2, R3 and R4, in the para position, all represent a tert-butyl or Si (Rio) 3 group. After removal of the tert-butyl or Si (Rio) 3 group, for example by the action of AlCl 3 in the presence of phenol, different substitutions can be obtained. Before functionalization and to allow a more selective functionalization of the phenyl groups, it is possible to oxidize at least a portion of the sulfur bridges, to form a group ûS (0) - or ûSO2-. The compounds according to the invention comprise three series of non-equivalent sulfur bridges, which makes it possible to obtain selective oxidations of the bridges to sulphoxides and / or sulphones. Such an oxidation can, for example, be carried out by the action of NOBF 4, for example in a chlorinated solvent such as chloroform or dichloromethane, in order to obtain X 1 and X 3 û S (O) -. The action of AlCl 3, KNO 3, in tetraethylene glycol dimethyl ether makes it possible, for its part, to obtain at X 3 a function û S (0) -. The action of a trifluoroacetic acid / nitric acid mixture in solvents of the hydrocarbon or halogenated hydrocarbon type, such as chloroform, makes it possible to oxidize all the positions X1 to x6 in the form of S (O) -. It is also possible to go from a SO2 function to a S (0) function and vice versa according to various methods described in the literature in the case of thianthrenes in particular. For example, the Journal of Organic Chemistry, 69 (26), 9090-9099 (2004) discloses SO 2 SO 2 oxidation on thianthrenes by the action of KMNO 4 in the presence of acetone.

  Compounds (Ie) in which X1 = X4 = X5 = X6 = SO2, can be obtained analogously to SCHEMA 1, starting from the oxidized thiacalixarene of formula (VII): R2 RR4 so sot (VII) Compound (VII) is prepared according to the method described by N. Iki et al, in Tetrahedron Letters, 39, 7559-7562 (1998). This method can be generalized in the case where X1 = X4 = X5 = X6 = S (0). Thiacalixarene is prepared according to the route described in N. Iki and Tetrahedron Letters, 39, 7559-7562 (1998) and N. Morohashi et al. Tetrahedron Letters, 41, 2933-2937 (2000).

  Phenyl groups also have three non-equivalent positions that may be differently substituted. The introduction of the substituents R 1, R 2, R 3 and / or R 4 can be carried out according to any appropriate technique. For example, bromination may be carried out by the action of Br2 or HBr, as described in H. Gilman et al., Journal of the American Chemical Society, 1958, 23, 313-314 or in H. Gilman and Journal of the American Chemical Society, 1955, 77, 5944-5947. Reference may also be made to this last reference for the introduction of groups R1, R2, R3 and / or R4 of the type -NO2, -NH2 or -NHCOR6, R8 being as defined previously for (I). When R 1, R 2, R 3 and R 4 all represent an Si (R 10) 3 group, these may be converted to a compound (I) wherein R 1, R 2, R 3 and R 4 all represent: - a bromine atom, by the action of Br 2, according to the method described by Felix Guy et al., Angewandte Chemie (1977), 89 (7), 502-4, an iodine atom per action of ICI, according to the method described by Felix Guy and Angewandte Chemie (1979), 91 (5), 439-2, - function CHO, by action of tBuOK in DMF, according to the method described by Effenberger Franz et al., Chemische Berichte (1985), 118 (10), 3900 The functional groups, optionally present in the compounds of formula (I), (Ia), (Ib), (Ic), (Id), (Ie), (If) and (Ig) and in the reaction intermediates may be protected, either permanently or temporarily, by protecting groups which provide an unambiguous synthesis of the expected compounds. The protection and deprotection reactions are carried out according to techniques well known to those skilled in the art. Those skilled in the art will be able to choose the appropriate protective groups. Compounds (I) are isolated and purified by conventional separation techniques. The compounds of formula (I) according to the invention are macrocycles of fairly rigid structure, which have a very high thermal stability and, moreover, offer many possibilities of interconversion. The compounds of formula (I) according to the invention exhibit, in particular, the following properties: good electronic delocalization of electrons Tc, high complexing properties, high thermal stability, which makes possible the heat treatment of these compounds and therefore their incorporation in materials, for example in a matrix of the glass type. In addition, the compounds are functionalized or easily functionalizable, which makes it possible to modulate their properties. The compounds according to the invention have a concave cavity. Such a cavity is capable of trapping molecules, so that the compounds according to the invention can be used in applications for extraction, trapping, recognition of molecules, for the formation of inclusion complexes in particular. The compounds of formula (I) according to the invention, and in particular those in which X1 = X2 = X3 = X4 = S, can be modified to form cationic radicals at the sulfur bridges X1, X2, X3 and / or X4 very stable. The structure thus obtained becomes flat, with a strong delocalisation of the charge, which can cause a change in color. The presence of thiacalixarenes stabilizes the flat shape.

  Such radicals can be prepared in different ways. By way of example, mention may be made of: an oxidation in an acidic medium, for example in the presence of sulfuric acid, a complexing with a Lewis acid, for example a metal salt, such as a Fe or Ti salt which, after reduction, allows oxidation of sulfur bridges, such complexes make it possible to stabilize the radicals obtained, - by electrochemical reaction. This reaction is particularly interesting because it is reversible and leads to electrochromic compounds. By selecting the bridge or bridges that will be oxidized to form a radical, it is possible to modulate the color of the complex that will be obtained. Such compounds find many applications, in particular as a pigment, optical switch or electronic. They can also be used as a probe or chemical sensor. If they are used as monomer in polymerization reactions or reactions involving a radical, they can lead to conductive polymers. The compounds of formula (I) according to the invention, as well as their complexes with metal salts, may also be used as optical limiters. They may be used for the manufacture of materials having optical limiter properties, for example, laser protection materials. They may be incorporated into glass matrices, using, for example, the sol-gel method (CJ Brinker, GW Scherer, Sol-Gel Science, The Physics and Chemistry of Sol-Gel Processing, Academic Press, 1990 and LC Klein. , Sol-Gel Optics: Processing and Applications, Kluwer Academic Publishers, 1994) to develop laser protection materials or light filters. The preparations which follow, with reference to the appended figures, illustrate the invention.

  FIG. 1 represents the electrochemical curve obtained with compound 2. FIG. 2 represents the spatial structure of compound 4 obtained by X-ray diffraction. FIG. 3 represents the spatial structure of compound 5 obtained by diffraction of X-ray. FIG. 4 represents the electrochemical curve of compound 5. FIG. 5 represents the spatial structure of compound 6 obtained by X-ray diffraction.

  Figure 6 shows the spatial structure of compound 7 obtained by X-ray diffraction. Figure 7 shows the spatial structure of compound 8 obtained by X-ray diffraction.

  FIG. 8 represents the electrochemical curve of compound 8. FIG. 9 is a UV-visible spectrum revealing a visible absorption band for a thiacalixthianthrene according to the invention in free radical form. The compounds were characterized by NMR, by elemental analysis and the solid state structure was determined by X-ray diffraction. Mass Spectrometry: Mass spectrometry results were accumulated on a Thermofinnigan LCQ Advantage instrument at ion trapping, detecting positive (+) or negative (-) ions in ESI mode. The samples (in the methanol: dichloromethane: water mixture, 45: 40: 15, v / v / v) were injected directly into the source (5 μl / min) using a syringe pump. The following parameters have been applied for the source: spray current 3.0-3.5 kV, nitrogen flow 5-20 (arbitrary units). The capillary is maintained at a temperature of 200 ° C. Nuclear Magnetic Resonance analyzes are performed on a Bruker AM300 spectrometer. The structures obtained by X-ray diffraction are made using a Nonius Kappa CCD diffractometer. Elemental analysis is performed at the CNRS central analysis service in Solaize (Vernaison). UV-Visible spectroscopy was performed on a Perkin Elmer Lambda 35 spectrometer. The electrochemical curves, ie the cyclic voltammetric curves, were obtained using a 262A EGG type potentiostat. The cells used are single compartment with a standard configuration with three electrodes. The reference electrode consists of a saturated calomel electrode (SCE). The counter electrode is a platinum wire electrode. The working electrode is a 1 mm platinum disk or a 3 mm glassy carbon disk. The solvent CH2Cl2 (99.8% anhydrous Aldrich) and the commercial NBu4BF4 (Fluka, purum) - NBu4PF6 (Fluka, puriss) electrolytes are used. The solutions are degassed with N2U nitrogen and stored under nitrogen during the experiments.

PREPARATION 1 Preparation of 5,11,17,23 tetra (tert-butyl) 25,26,27,28-tetrakis- (0) dimethylthiocarbamoylthiacalix [4] arene, compound 1 (CH3) 2NCSCI, Cs2CO3 SOOOO (1) / N4 A dispersion of 3.00 g (4.16 mmol) of 5,11,17,23tetra (tert-butyl) -25,26,27,28-tetrahydroxyythiacalix [4] arene (prepared according to Tetrahedron Letters, 1997, 38 (22), 3971, 3972) in acetone, 3.1 g (24.97 mmol) of (CH3) 2NCSCI are added, followed by 3.5 g (24.97 mmol) of K2CO3. . The reaction mixture is stirred at 50 ° C. for 24 hours, the acetone is evaporated and the residue is dissolved in 50 ml of 1M HCl and 100 ml of dichloromethane.

  The organic phase is separated and the aqueous phase is extracted three times with dichloromethane. The organic phases are combined and filtered on filter paper and then concentrated under vacuum until 30 ml of product are obtained. The product obtained is then precipitated in 50 ml of methanol and sintered.

  NMR analysis shows that the product obtained is composed of 85% of the alternating 1,3-conformer and 15% of the 1,2-conformer (Hosseini et al in Journal of Supramolecular Chemistry, 2002, 2, 21). 1H NMR (CDCl3, 300 MHz) in ppm: 1,3-alternated 7.49 (s, Ar-H, 8H), 3.44 (s, NCH3 12H), 2.28 (s, N-CH3 , 12H), 1.30 (s, tBu, 36H) 1.2-alternating 7.76 (d, J = 0.008 ppm, Ar-H, 4H), 7.57 (d, J = 0.008 ppm) , Ar-H, 4H), 3.24 (bs, N-CH3, 12H), 2.28 (bs, N-CH3, 12H), 1.36 (s, tBu, 36H) Compound 1 can also be prepared as follows: To a dispersion of 10 g (13.8 mmol) of 5,11,17,23tetra (tert-butyl) -25,26,27,28-tetra-hydroxythiacalix [4] arene in 200 ml of acetone, 11.5 g (83.2 mmol) K2CO3 and 10.5 g (83.2 mmol) (CH3) 2NSCI are added. The reaction mixture is refluxed under argon for 48 hours, then poured onto water and neutralized with hydrochloric acid. The suspension is filtered and the solid obtained is washed 5 times with methanol and then dried. 12.1 g (yield = 81%) of a beige product is obtained, containing according to the NMR analysis 80% of the alternating conformer 1.3 and 20% of the alternating conformer 1.2. The product thus obtained is used directly, without further purification, in PREPARATION 2.

PREPARATION 2 Preparation of 5,11,17,23-tetra- (tert-butyl) thiacalix [2-thianthrene, compound 2 (1) (2) 52 mg (0.048 mmol) of compound 1 prepared according to PREPARATION 1 are placed in a nacelle of glass, itself positioned in a tubular furnace. Heating under an argon atmosphere is then carried out as follows: heating up to 310 ° C. for a period of 120 minutes, keeping at 310 ° C. for 20 hours. 26 mg (yield = 75%) of a black residue are obtained whose NMR analysis proves the purity. Chromatography on a silica column eluting with a CH2Cl2 / pentane mixture, 1/1, v / v gives 16 mg (yield = 46%) of white powder. 1 H NMR (CDCl 3, 300 MHz) in ppm: 7.73 (d, J = 2.3 Hz, Ar-H, 4H), 7.46 (d, J = 2.3 Hz, Ar-H, 4H), 1.26 (s, tBu, 36H) Elemental analysis, percent found (% calculated): C 64.91 (64.37) H 6.84 (6.41) S 24.02 (24, 54). The electrochemical tests carried out are illustrated in FIG. 1 and show that two oxidation waves are observed at 1.2 and 1.5 volts and that a third is also detected at about 2 volts. The first two waves correspond to the oxidation of the sulfur bridges of the thianthrene skeletons leading to the formation of radicals at the level of the sulfur atoms. Both thianthrene structures are oxidized at two different potentials. Compound 2 can also be prepared as follows: 5 g of the compound prepared according to PREPARATION 1 are placed in a Schlenk tube and heated to 410 ° C for about 3 minutes, until the starting material is under form of a dark liquid boiling. Then, the resulting liquid is cooled to room temperature and the resulting black mass is dissolved in 60 ml of chloroform. The solution obtained is filtered, concentrated under reduced pressure and then precipitated with methanol. The precipitate obtained is washed thoroughly, first with acetone and then with diethyl ether. The resulting residue is then purified by filtration on a silica gel column using a mixture of chloroform / cyclohexane 1/1, v / v as eluent. 1.2 g (yield = 36%) of a white powder is obtained.

PREPARATION 3 25,26,27,28-Tetrakis (0) dimethylthiocarbamoylthiacalix [4-larene, Compound 3 (CH3) 2NCSCI Cs2CO3 O 0 ~ N ~ N` NRI (3) To a dispersion of 2 g (4, 03 mmol) of 25,26,27,28-tetrahydroxythiacalix [4] arene (prepared according to Tetrahedron Letters, 1998, 39, 2311-2314) in acetone, 2.98 g (24.16 mmol) of (CH3) 2NCSCI are added, followed by 7.84 g (24.16 mmol) of Cs2CO3. The reaction mixture is stirred at 50 ° C. for 48 hours, then the acetone is evaporated and the residue is dissolved in 50 ml of 1M HCl and 50 ml of dichloromethane. The organic phase is separated and the aqueous phase is extracted three times with chloroform.

  The organic phases are filtered on filter paper, concentrated under reduced pressure. After a slight addition of methanol in the solution, 0.5 g (yield = 15%) of pure product are isolated. 1H NMR (CDCl3, TMS, 300 MHz) in ppm: 7.46 (d, 3 = 8 Hz, 8H, Ar-H), 6.99 (t, 5.3 = 7.2 Hz, Ar-H, 4H), 3.4 (s, 12H, N-CH3), 2.39 (s, 12H, N-CH3)

  PREPARATION 4 Preparation of thiacalix [2] thianthrene, compound 4 a) (3) 300 C 0.1 g of compound 3 prepared in PREPARATION 3 is placed in a glass nacelle itself placed in a tubular furnace. Heating under a nitrogen atmosphere is then carried out: heating up to 310 ° C. for 120 minutes, then maintaining at 310 ° C. for 20 hours. The black residue obtained is extracted with 30 ml of chloroform, and the product is isolated after chromatography on a silica column, eluting with a mixture of petroleum ether / chloroform, 1/1, v / v. 0.1 g (yield = 17%) of white product is then isolated.

  B) PhOH, AlCl 3 40% (2) (4) 0.15 g (0.2788 mmol) of the compound prepared in paragraph a) are suspended in 30 ml of toluene, 0.3 g (3.067 mmol) of phenol and 1.3 g (10.0 mmol) of AlCl 3 are added, carefully, with vigorous stirring. The reaction mixture is then refluxed for 48 hours. The black solution obtained is allowed to cool to room temperature and is carefully poured into 200 ml of water. After stirring for two hours, the organic phase is separated. About three-quarters of toluene is distilled off and methanol is added to the concentrated toluene solution. After stirring for one hour, the suspension is filtered. The residue obtained is washed with methanol and acetone. The isolated product is in the form of a beige powder (40 mg, yield = 40 h).

  1H NMR (CDCl3, TMS, 300 MHz) in ppm: 7.58 (d, J = 7.5Hz, 1H, Ar-H), 7.43 (d, J = 7.5Hz, 1H, Ar-H), 7.12 (t, J = 7.5 Hz, 1H, Ar-H) MS (ESI): calculated: 491.92, found: 493.0 (MH +) FIG. in the space of compound 4 obtained by X-ray diffraction.

PREPARATION 5 Preparation of 5,11,17,23-tetra- (tert-butyl) thiacalixiflianthrene disulfoxide, compound 5 NOBF4 (2) (5) 20 mg (2.8.10-5 mol) of compound 2 prepared in PREPARATION 2 are dissolved in 10 ml of chloroform and 20 mg of NOBF 4 (1.71 × 10 -4 mol) are added The reaction mixture is stirred for about 12 hours at room temperature until the blue color disappears. the crude product is purified by chromatography on a silica column, eluting with a chloroform / acetone mixture, 10/1, v / v and 20 mg (yield = 95%) of white solid are obtained.1H NMR (CDCl3, 300 MHz) in ppm: 8.07 (d, 3 = 2.1 Hz, Ar-H, 2H), 7.91 (d, J = 2.1 Hz, Ar-H, 2H), 7.83 (d , 3 = 2.1 Hz, Ar-H, 2H), 7.76 (d, J = 2.1 Hz, Ar-H, 2H), 1.12 (s, t-Bu, 16H). , 1.19 (s, t-Bu, 16H) MS (ESI): calculated: 748.16, found: 749.2 (MH +) FIG. 3 represents the spatial structure of the compound obtained by diffraction of X-rays.

  Figure 4 shows the electrochemical curve of compound 5: no oxidation wave is observed.

  PREPARATION 6 Preparation of thiacalix [2] thianthrène sulfoxide, compound 6 s AICI3, KNO3, tetraglyme (4) (6) 72 mg (1.46.10-4 mol) of compound 4 obtained in PREPARATION 4 are dissolved in 10 ml of chloroform and 0.5 ml of tetraethylene glycol dimethyl ether, 0.1 g (1.10-3 mol) of KNO3 and 0.11 g (8.10-4 mol) of AlCl 3 are added.

  The reaction mixture is refluxed for 12 hours. Chloroform is evaporated and the resulting suspension is dissolved in methanol and filtered. The solid obtained is purified by chromatography on a column of silica gel, eluting with chloroform.

  The expected product is isolated with a yield of 20% (15 mg). 1H NMR (CDCl3, TMS, 300 MHz) in ppm: 7.87 (d, 3 = 7.8 Hz, 2H, Ar-H), 7.75 (d, J = 7.8 Hz, 2H, Ar-H), 7.45 (d, 3 = 7.8 Hz, 2H, Ar-H), 7.34 (t, J = 7.8 Hz, 2H, Ar-H), 7.25. (t, 3 = 7.8 Hz, 2H, Ar-H) MS (ESI): calcd: 507.92, found: 509.0 (MH +) Figure 5 shows the spatial structure of compound 6 obtained by X-ray diffraction.

PREPARATION 7 Preparation of 5,11,17,23-tetra- (tert-butyl) thiacalixf 2] thianthrene hexasulfoxide, compound 7 (2) (7) 50 mg (1.46 x 10 -4 mol) of compound 2 is dissolved in 5 1 ml of chloroform and 2 ml of trifluoroacetic acid and 3 ml of 100% nitric acid are added. The reaction mixture is stirred at room temperature for 24 hours, then poured into water, extracted with chloroform and evaporated under reduced pressure.

  A solid containing the two isomers in a 1: 1 ratio is purified by crystallization by slow evaporation of an ethanol / chloroform solution to give 20 mg of pure compound 7 (yield = 35%) 1 H NMR (CDCl3, TMS, 300 MHz ) in ppm: 8.53 (d, 3 = 2.1 Hz, 4H, Ar-H), 8.35 (d, J = 2.1 Hz, 4H, Ar-H), 1.4 ( s, 36 H, tBu) Figure 6 shows the spatial structure of compound 7 obtained by X-ray diffraction.

  Preparation of 5,11,17,23-tetra- (tert-butyl) thiacalixiflianthrene tetrasulfone compound 8 SO 2 S02 (CH3) 2NCSCI K2CO3 to a dispersion of 10 g (11.8 mmol) of 5,11,17, 23tetetra (tert-butyl) θthiacalix [4] arenetetrasulfone (N. Iki et al., Tetrahedron Letters, 39, 7559-7562 (1998)) in 200 ml of acetone, 10 g (70.6 mmol) of K 2 CO 3 and 9 (70.6 mmol) of (CH3) 2NCSCI are added. The reaction mixture is heated under reflux under argon for 48 hours, then poured onto water and neutralized with HCl until a slightly acidic solution is obtained. The suspension obtained is filtered, the isolated solid is washed 5 times with methanol and then dried. 11.7 g (yield = 82%) of a white product are obtained. 1H NMR (CDCl3, 300 MHz) in ppm: 8.47 (s, Ar-H, 8H), 3.39 (s, N-CH3, 12H), 2.29 (s, N-CH3, 12H), 1.39 (s, tBu, 36H) MS (ESI): calculated: 1196.25 found: 1197.0 (MH +) b) nS 2 SO 2 (8) 5 g of the product obtained from ) are placed in a Schlenk tube and heated to 410 ° C in air for approximately 3 minutes (until the starting compound is in the form of a dark boiling liquid). The reaction mixture is then cooled to room temperature and the black solid mass is dissolved in 60 ml of chloroform. The solution is filtered and evaporated to dryness under reduced pressure. The product obtained is then purified by chromatography on a column of silica gel, eluting with a 10/1 (v / v) chloroform / acetone mixture. The product obtained is recrystallized from chloroform / ethanol to give 140 mg (yield = 4%) of compound 1H NMR (CDCl3, 300 MHz) in ppm: 8.33 (s, Ar-H, 4H) , 8.20 (d, J = 2.1 Hz, Ar-H, 2H), 8.16 (d, 3 = 2.1 Hz, Ar-H, 2H), 1.34 (s, tBu). Figure 7 shows the spatial structure of compound 8 obtained by X-ray diffraction.

  FIG. 8 represents the electrochemical curve of compound 8: only the reduction of bridges is observed between -1 and -2 V. Preparation of 5,11,17,23-tetra- (trimethyl / si / yl) thiacalix [21 thianthrene, compound ## EQU1 ## 28-tetra-hydroxythiacalix [4] arene in 30 ml of acetone, 1 g (7.24 mmol) K 2 CO 3 and 0.9 g (7.24 mmol) (CH 3) 2 NCSCI are added. The reaction mixture was refluxed under argon for 48 hours, then poured onto water and neutralized with hydrochloric acid. The suspension is filtered and the solid obtained is washed 5 times with methanol and then dried. 0.9 g (yield = 65%) of a yellow product is obtained. 1H NMR (CDCl3: 300 MHz): 7.64 (s, Ar-H, 8H), 3.54 (s, N-CH3, 12H), 2.72 (s, 1H-CH3 12H). ) b) 20 t-, (0 1) tert.BuLi I`, ~ 2) TMSCI S 0 00 0 ~ s \ s / N / N. ## EQU1 ## 0.56 g (0.5 mmol) of 5,11,17,23 tetrabromium25,26,27,28-tetra- ( 0) -thiocarbamoylcalixarene are dispersed in 20 ml of anhydrous THF and the suspension is cooled to -78 C. 12 ml of a 1.7 M solution of tert-butyllithium in pentane (20.4 mmol) is added dropwise and the mixture is stirred cold for 90 minutes. 2.6 ml (20.4 mmol) of trimethylsilylchloride are added and the reaction medium is left at room temperature for 12 hours. It is then poured into a 1 N HCl solution and extracted with chloroform. The organic phase is dried over concentrated MgSO4 and precipitated with methanol. 0.28 g (55%) of expected product are obtained.

  1H NMR (CDCl3, 300 MHz): 7.60 (s, Ar-H, 8H), 3.44 (s, N-CH3, 12H), 2.23 (s, N-CH3 12H ), 0.27 (s, Si-Me, 36H) MS (ESI): calculated: 1132.1 found: 1133.0 (MIt) c)

  Si-Complexation tests a) Preparation of complexes of 5,11,17,23-tetra- (tertbutyl) thiacalix [2] thianthrene, compound 2 with iodine or bromine The complexes are prepared by slow evaporation of a thiacalix solution [2] of thianthrene (compound 2) and iodine or bromine (2 equivalents of iodine or bromine for one equivalent of compound 2) in chloroform. The reaction with Cl2 leads to oxidized thianthrenes (disulphoxide). b) Preparation of a thiacalix [2] thianthrene complex with iodine This complex is prepared in a manner analogous to the preceding complexes, using toluene as a solvent. Thianthrene has the 1,2-alternating conformation. These tests a) and b) validate the thiacalix [2] thianthrenes ability according to the invention to complex or trap other molecules, which is of interest for applications in catalysis or extraction, in particular. c) 5,11,17,23-tetra- (tert-butyl) thiacalix [2] thianthrene radicals and OSS complexes psi 10 mg of 5,11,17,23-tetra- (trimethyl / si / y) thiacalix [2] thianthrene are heated at 400 ° C for 1 minute. The brown solid obtained is dissolved in chloroform and filtered. After evaporation of the solvent, the compound 9 is obtained. MS (ESI): calculated: 781.09 found: 782.0 (MHe) of these radicals with iron chloride. Figure 9 shows the absorption as a function of the wavelength of a tetraterlbutylthiacalix [2] thianthrene (compound 2) at 10-4 mol / l in chloroform, as well as the curve obtained with the radical formed from this same compound 2 to 10-4 mol / I in chloroform, by electrochemistry after application of the voltammetry cycle. No absorption is observed in the visible for compound 2 (curve A) while an absorption band at 575 nm is observed for its radical (curve B).

  A radical is also formed by dissolving the compound 2 in a concentrated sulfuric acid solution. The same absorption curve is obtained. The complex of a radical of compound 2 is obtained from a solution in chloroform containing 10-3 mol / l of compound 2 and 10-2 mol / l of FeCl 3. After 10 minutes' stirring of the reaction mixture under nitrogen, UV-visible spectroscopy shows the appearance for the radical compound 2 / Fe (III) of the same absorption band as that obtained previously for the radical of compound 2 The solution of compound 2, which was initially colorless, takes a blue color with formation of the radical or of a radical / Fe (III) complex.

Claims (9)

  1 - Compounds of formula (I): in which: X1, X2, X3, X4, X5 and X6, identical or different, each independently represent a sulfur atom, ùS (O) - or -SO2-, - ni , n2, n3 and n4, identical or different, are each equal to 1, 2 or 3, - R1, R2, R3 and R4, which are identical or different, each independently represent: - a hydrogen atom, - an atom of halogen, - a (C1-C6) alkyl, phenyl group, - an optionally substituted phenylazo group, preferably in position 4 with a nitro group, - a group -N = CHR5 in which R5 represents a (C1-C4) group alkyl, pyridyl or phenyl, a -C-C-R 6 group in which R 6 represents a hydrogen atom, a (C 1 -C 4) alkyl, tri (C 1 -C 4) alkylsilyl or phenyl group, a nitro group; a group -NHR7, in which R7 represents a hydrogen atom or a -C (O) R8 group with R8 chosen from a (C1-C4) alkyl, pyridyl, phenyl and halogen atoms group; group -C (0) R9 with R9 representing a hydrogen or halogen atom or a -OH, (C1-C4) alkyl, aryl, or O-alkyl group, --Si (R10) 3 group with R10 which represents a hydrogen atom or a group (C1-C4) alkyl or aryl; -C (R11) = C (R12) (R13) with R11, R12, R13, which may be identical or different, each of which independently represents a hydrogen atom (I); or halogen or a (C1-C4) alkyl, aryl or O-alkyl group, as well as their salts, solvates and hydrates.   2 - Compounds according to claim 1 wherein at least one of the bridges X1, X2, X3, X4 represents a sulfur atom.   3 - Compounds according to claim 1 or 2 of formula (Ia): s (R1 ~ n1 ll ~ (R2 ~ n2 (Ia) wherein X5, X6, R1, R2, R3 and R4, ni, n2, n3 and n4 are as defined in claim 1. 10   4 - Compounds according to claim 3 characterized in that X5 = X6 = S.   5 - Compounds according to claim 1 of formula (Ib): (Ib) wherein X3, X4, X5, X6, R1, R2, R3 and R4, n1, n2, n3 and n4 are as defined in claim 1. 15   6 - Compounds according to claim 1 of formula (Ic): (Ic) wherein X1r X2, X5, X6, R1, R2, R3 and R4, n1, n2, n3 and n4 are as defined in claim 1.   7 - Compounds according to claim 1 of formula (Id): x (Id) in which X1, X2, X3, X4, R1, R2, R3 and R4, n1, n2, n3 and n4 are as defined in claim 1 .   8 - Compounds according to claim 7 characterized in that X1 = X3 = -S (0) -and X2 = X4 = S.   9 - Compounds according to claim 7 characterized in that X1 = X2 = X4 = S and X3 = -S (0) -. - Compounds according to claim 1 of formula (Ie): x (Ie) wherein X1, X4, X5, X6, R1, R2, R3 and R4, n1, n2, n3 and n4 are as defined in claim 1. , preferably X1 = X4 = X5 = X6 = SO2. 11 - Compounds according to claim 1 of formula (If): (If) in which X1, X2, X3, X4, R1, R2, R3 and R4, n1, n2, n3 and n4 are as defined in claim 1. 1012 - Compounds according to claim 1 of the formulas (Ig): n0 4 '31n3 SO2 (Ig) in which X5, X6, R1, R2, R3 and R4, n1, n2, n3 and n4 are as defined for claim 1. -Composés according to one of claims 1 to 12 characterized in that R1 = R2 = R3 = R4. 14 - Compounds according to one of claims 1 to 13 characterized in that 10 n1 = n2 = n3 = n4 = 1. 15 - Compounds according to one of claims 1 to 14 characterized in that R1, R2, R3 and R4 substitute the para position of the phenyl. 16 - Compounds according to one of claims 1 to 14 characterized in that R1, R2, R3 and R4 are identical and represent a hydrogen atom, a tert-butyl group or a trimethylsilyl group. 17 - Cationic radicals of a compound according to one of claims 1 to 16 wherein at least one of the bridges X1, X2, X3, X4, represents a sulfur atom, obtained by exchange of at least 1 electron. 18 - Radicals according to claim 17 of formula (IIa): (IIa) wherein X5, X6, R1, R2, R3 and R4, n1, n2, n3 and n4 are as defined in claim 1 and 1, 2, 3 or 4 of the bridges X'1, X'2, X'3 and X'4 represents a radical 20S + '-, the others representing a sulfur atom. 19 - Metal complexes of a compound according to one of claims 1 to 18. 20 - Complexes according to claim 19 characterized in that the metal is selected from alkali metals, transition metals, lanthanides and actinides. 21 - Complexes according to claim 20 characterized in that the metal is selected from cesium, titanium, iron, copper, palladium, mercury, gold and more preferably, silver, zinc, or platinum.