Preparation method of perfluorocyclobutane-containing monomer

Abstract

The present invention relates to a multi-step process for preparing polyfunctional aromatic compounds containing two benzene rings with reactive groups susceptible to polycondensation reactions to provide polycondensation polymers, using economical raw materials and having high selectivity and overall yield.

Description

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS

[0002] This application claims the benefit of Indian Provisional Application No. 201921018845 filed on May 10, 2019, the entire contents of which are incorporated herein by reference for all purposes. Technical Field

[0003] The present invention relates to a method for preparing a perfluorocyclobutane-containing monomer, certain perfluorocyclobutane-containing monomers prepared therefrom, and a method for preparing a polymer using the same. Background Art

[0004] Extensive research has been conducted in the past on perfluorocyclobutyl (PFCB) aryl ether polymers, which are produced by thermal [2π+2π] cyclodimerization of aryl trifluorovinyl ether monomers or by polycondensation of perfluorocyclobutyl aryl ether dimer difunctional intermediates, as notably explained in IACONO, Scott T et al., Science and Technology of Perfluorocyclobutyl Aryl Ether Polymers. J. Polym. Sci. Part A: Polym. Chem. 2007, Vol. 45, No. 5705-5721.

[0005] One of the key aspects to the success of PFCB aryl ether polymer-based processes in this area is the availability of monomers and intermediates with a purity suitable for use in polycondensation reactions through economically viable processes using potentially readily available and inexpensive chemicals as feedstocks and applying high yield / high selectivity chemistries.

[0006] For example, US 5021602 (THE DOW CHEMICAL COMPANY) 4.06.1991 describes a process for preparing a compound having the formula:

[0007] wherein R and R' are groups connected to the perfluorocyclobutane ring through the molecular structures X and X', in particular, R and R' are phenylene, and X and X' are -O- parts of ethers; G and G' are any reactive groups, wherein n and n' are integers, and the compound is represented by the formula G n -RX-CF=CF 2 The present invention relates to a method for preparing a fluoroethylene-based compound by dimerization of a functional perfluorovinyl compound of the present invention, wherein these latter compounds are preferably formed by a process comprising the steps of:

[0008] (a) forming a compound having the formula (G")n -RX - wherein G" is a functional group G or a group susceptible to modification to produce a group G;

[0009] (b) reacting the salt with a compound of formula Q-CF 2 -CF 2 -Q, wherein at least one Q is iodine or bromine, and the rest are chlorine, iodine or bromine, to obtain a 1,2-dihalo-1,1,2,2-tetrafluoroethane having the formula (G") n -RX-CF 2 -CF 2 -Q compound; and

[0010] (c) dehalogenating the latter compound in the presence of a metal reagent such as Zn or Mg.

[0011] The process for introducing the trifluorovinyl group in the precursor into the perfluorocyclobutyl derivative involves the use of expensive halogen / fluorine derivatives in a sequence of nucleophilic substitution and subsequent dehalogenation, which may affect the overall yield of the process, and which may result in the presence of bromine / iodine-containing by-products in the final perfluorocyclobutyl derivative, which may negatively affect its reactivity as a monomer, and / or the properties / thermal stability of the polymer obtained therefrom.

[0012] An alternative method for producing perfluorocyclobutane-containing compounds is provided in US 5442030 (E.I. Dupont de Nemours and Company) 15.08.1995, in which the PFCB ring is directly bonded to the aromatic carbon of the adjacent benzene ring via a C-C bond. 3 ) 4 The product obtained by adding p-nitro or m-nitroiodobenzene and Zn to iodotrifluoroethylene under catalysis is reacted to obtain the corresponding formula CF 2 =CF-Φ-NO 2 trifluorovinyl compounds, wherein Φ is phenyl, which is dimerized to O 2 N-Φ-PFCB-Φ-NO 2 (where PFCB is perfluorocyclobutane), and then by reacting with SnCl 2 / NaBH 4 However, the electron-withdrawing effect exerted by the nitro group on the PFCB moiety directly bound to the aromatic carbon leads to at least partial defluorination of the PFCB group, thereby generating a perfluorocyclobutene moiety.

[0013] There remains a need in the art for efficient methods of preparing perfluorocyclobutyl-diaryl ether monomers, starting from readily and economically available precursors and producing compounds with high purity and high yield. Summary of the invention

[0014] Therefore, the present invention relates to a method for preparing a compound having the general formula [Formula (I)]:

[0015] wherein each G and G', being the same or different from each other, are independently selected from the group consisting of

[0016] - halogen selected from F, Cl, Br, I, in particular -F, -Cl;

[0017] --NR H 1 R H 2 , where R H 1 and R H 2 independently H or C 1 -C 6 Hydrocarbyl, preferably H;

[0018] --OH;

[0019] -a nitrile group having the formula -CN and a nitrile group having the formula -NO 2 of nitro;

[0020] --COY, wherein Y is -X, X is a halogen selected from F, Cl, Br, I, in particular -F, -Cl; -OH; -OR H 3 、-NR H 1 R H 2 , where R H 3 It is C 1 -C 12 Hydrocarbon groups, especially C 1 -C 6 Alkyl or C 6 -C 12 aryl; and R H 1 and R H 2 has the meaning detailed above; preferably Y is OH;

[0021] --SO 2 Y', wherein Y' is -OH or -X', X' is a halogen selected from F, Cl, Br, I, in particular -F, -Cl;

[0022] --E-Ar-X", where X" is hydrogen, -OH, -X°°, -C(O)X # , where X #is -OH or -X°; wherein X°° is a halogen selected from F, Cl, Br, I, in particular -F, -Cl; -E- is a divalent bridging group selected from the group consisting of: a bond, C 1 -C 6 Exemplary embodiments of carbon-containing bridging groups; sulfur-containing bridging groups; -E- are notably: -(CH 2 ) m -, wherein m is an integer from 1 to 3; -C(O)-, -C(CH 3 ) 2 -, and -SO 2 -; -Ar- is a divalent aromatic group, in particular (optionally substituted) phenyl (-Ph-), for example, wherein the connecting bonds in -Ph- may be in the ortho-, meta- or para-position relative to each other, preferably in the para-position,

[0023]

[0024] -With style A group in which X z Yes-NH 2 ;-NO 2 ; -OH, -X°°, -C(O)X # , where X # is -OH or -X°; wherein X°° is a halogen selected from F, Cl, Br, I, in particular -F, -Cl;

[0025] - each n, identical or different from each other, is an integer from 1 to 3, preferably from 1 to 2, more preferably n=1,

[0026] The method comprises:

[0027] Step (a): an anion having the formula [Formula (II)]:

[0028]

[0029] wherein G" is a group G or G' as described above, or a precursor thereof, reacted with tetrafluoroethylene at a temperature of up to 115°C and a pressure of at least 4 bar to obtain a compound of formula (III):

[0030]

[0031] Step (b): a step of dimerizing at least one compound of formula (III) obtained from step (a) by heat treatment at a temperature exceeding 150° C. to obtain a compound of formula (IV):

[0032]

[0033] wherein G" and G'" are each a group G or G' as described above, or a precursor thereof, it being understood that when G" and G'" are a group G or G' as described above, the compound of formula (IV) meets the requirements of the compound of formula (I); and

[0034] Step (c): Optionally, a step of reacting a compound of formula (IV) under appropriate conditions to convert the precursor groups G" and G"' of formula (IV) into groups G and G' to obtain the above compound of formula (I).

[0035] Applicants have surprisingly found that the above process is effective in providing high yields of compound (I), which is notably useful as a monomer for polycondensation reactions, as detailed above, using cheap and readily available tetrafluoroethylene acting on the synthon of a perfluorocyclobutane group, said process providing the target compound in high yields and free of brominated and iodinated impurities having said halogen in the perfluorocyclobutane ring. DETAILED DESCRIPTION

[0036] As mentioned above, the process of the present invention is used to prepare compounds having formula (I) as detailed above, which, as detailed above, contain at least one functional group G or G' on each benzene ring of said formula (I). Although more than one functional group may be present, it is generally believed that the best performance is obtained when each n is 1, that is, formula (I) has only one functional group on each benzene ring.

[0037] As mentioned above, G and G' are independently selected from the functional moieties listed above, which can be advantageously used to polymerize compound (I) in polycondensation or other types of reactions, or to further modify it, with a view to possible incorporation into the polymer chain.

[0038] The choice of the nature of the group G or G' will depend on the use of the molecule (I): in particular, since compounds of formula (I) have demonstrated use as monomers for incorporation into polycondensation polymers, the nature of the group will depend on the targeted properties of the polycondensation polymer.

[0039] For example, when seeking monomers suitable for incorporation into polyimide, polyamide, polyamideimide structures, in compounds having formula (I), G and G' may advantageously be -NR H 1 R H 2 , where R H 1 and R H 2 independently H or C 1 -C 6 Hydrocarbyl, preferably H; - having the formula A group in which X zYes-NH 2 .

[0040] When looking for monomers suitable for incorporation into polyamide, polybenzoxazole, polyester structures, G and G' may advantageously be:

[0041] -COY group, wherein Y is -X, X is a halogen selected from F, Cl, Br, I, in particular -F, -Cl; -OH; -OR H 3 、-NR H 1 R H 2 , where R H 3 It is C 1 -C 12 Hydrocarbon groups, especially C 1 -C 6 Alkyl or C 1 -C 12 aryl; and R H 1 and R H 2 has the meaning detailed above; preferably Y is OH;

[0042] - a cyano group of formula -CN; or

[0043] --OH.

[0044] When looking for monomers suitable for incorporation into the polyarylene ether structure, G and G' may advantageously be -OH; monomers having the formula -SO 2 Y', wherein Y' is -OH or -X', X' is a halogen selected from F, Cl, Br, I, in particular -F, -Cl; or a group -E-Ar-X", as detailed above.

[0045] In particular, when looking for monomers that are particularly suitable for incorporation into the poly(arylethersulfone) structure, G and G' may be selected from the formula -SO 2 Y', wherein Y' is -OH or -X', X' is a halogen selected from F, Cl, Br, I, in particular -F, -Cl; and selected from the group -E-Ar-X", as detailed above, wherein E is -SO 2 -, and X" is -OH or a halogen selected from F and Cl.

[0046] Typically, the process of the invention will therefore be used to prepare compounds of formula (Ia):

[0047] wherein G and G' are in the para position on the aromatic ring. For the compound of formula (Ia), it is further preferred that G and G' are the same.

[0048] Certain compounds of formula (I) as described in detail above are novel and are a further object of the present invention. In particular, compounds of formula (I) (and preferably formula (Ia)) wherein G and G' are:

[0049] (A) - a group of the formula -E-Ar-X" wherein X" is hydrogen, -OH, -X°, -C(O)X # , where X # is -OH or -X°; wherein X°° is a halogen selected from Cl, Br, I, in particular -Cl; -E- is a divalent bridging group selected from the group consisting of: a bond, C 1 -C 6 Exemplary embodiments of carbon-containing bridging groups or sulfur-containing bridging groups (-E-) are notably: -(CH 2 ) m -, wherein m is an integer from 1 to 3; -C(O)-, -C(CH 3 ) 2 -and-SO 2 -);or

[0050] (B)-Has the formula wherein X" is hydrogen, -OH, -X°°, -C(O)X # , where X # is -OH or -X°; wherein X°° is a halogen selected from F, Cl, Br, I, in particular -F, -Cl;

[0051] This is another object of the present invention.

[0052] Exemplary embodiments of the compounds of the invention are notably:

[0053] Compound (Ii) having the following formula:

[0054] Compound (I-ii) having the following formula:

[0055] Compound (I-iii) having the following formula:

[0056] Compound (I-iv) having the following formula:

[0057] A compound (Iv) having the following formula:

[0058] Compound (I-vi) having the following formula:

[0059] Compound (I-vii) having the following formula:

[0060]

[0061] Compound (I-viii) having the following formula:

[0062]

[0063] A compound (I-ix) having the following formula:

[0064]

[0065] A compound (Ix) having the formula:

[0066]

[0067] A compound (I-xi) having the following formula:

[0068]

[0069] All of these compounds can be used as monomers / precursors for the preparation of poly(aryletherketones), poly(arylethersulfones), benzoxazoles, polyimides, and the like.

[0070] As described above, in the first step of the present invention, an anion having the formula (II) is reacted with tetrafluoroethylene.

[0071] As described above, in the compound having formula (II), G" is a group of formula G or G' as described above, or a precursor thereof. The latter expression should be interpreted as meaning that, when the group G" is different from the target groups G and G' in the method of the present invention, the precursor group is meant to represent a group that can be converted into the target group G or G' of formula (I) by appropriate chemistry.

[0072] When G" is a group G or G', the process of the present invention obtains the target product having formula (I) by the sequence of steps (a) and (b), as described in detail above.

[0073] Exemplary embodiments of the G" group according to this variant are notably halogens selected from F, Cl, Br, I, in particular -F, -Cl.

[0074] When G" is different from groups G and G', the choice of group G" will therefore depend on the target groups G / G' intended to be contained in the compound (I) to be prepared, as well as on the functionalization chemistry underlying step (c), which therefore becomes an obligatory additional step of the process of the invention.

[0075] Exemplary embodiments of the G" group according to this variant are notably:

[0076] -hydrogen;

[0077] - halogen selected from F, Cl, Br, I, in particular -F, -Cl;

[0078] -C 1 -C 3 Alkyl groups, especially methyl groups (-CH 3 );

[0079] -C 1 -C 3 Alkoxy, especially of the formula -OR alk A group in which R alk It is C 1 -C 3 Alkyl groups, especially those of the formula -OCH 3 The group.

[0080] When G" is hydrogen, step (c) advantageously comprises at least one step selected from the group consisting of:

[0081] - Step (C-1): electrophilic aromatic substitution, wherein the hydrogen G" atom is reacted preferably in the presence of a Lewis acid with an electrophilic reagent selected from the group consisting of:

[0082] (i)XR' hyc Reactants, where X = Cl, Br, which bind to R' hyc sp of the group 3 -hybridized carbon, and R' hyc Is the sp 3 -Hybridized carbon C 1 -C 18 The hydrocarbon group may be substituted and may contain one or more groups of the formula: -(CH 2 ) m -, wherein m is an integer from 1 to 3; -C(O)-, -C(CH 3 ) 2 -and-SO 2 -, and it may contain one or more aromatic groups; the reaction can give a compound of formula (I) having the formula -R as detailed above hyc The group G / G'; R' hyc Oxidation of the side groups can give compounds of formula (I) having a group G / G'; R' of the formula -COY as detailed above hyc Suitable selection of the groups may give compounds of formula (I) having a group G / G' of the formula -E-Ar-X" as detailed above, wherein -E- contains sp 3 - Hybridized carbon;

[0083] (ii) XC(O)-R” hyc Reactants, where X = Cl, Br, and R"hyc It is C 1 -C 18 The hydrocarbon group may be substituted and may contain one or more groups of the formula: -(CH 2 ) m -, wherein m is an integer from 1 to 3; -C(O)-, -C(CH 3 ) 2 -and-SO 2 -, and it may contain one or more aromatic groups; the reaction can give a compound of formula (I) having the formula -C(O)-R" as detailed above hyc The group G / G'; R' hyc Suitable selection of the groups can give compounds of formula (I) having a group G / G' of the formula -E-Ar-X" as detailed above, wherein -E- is a -C(O)- group;

[0084] (iii)X-SO 2 -R * hyc Reactants, where X = Cl, Br, and R * hyc It is C 1 -C 18 The hydrocarbon group may be substituted and may contain one or more groups of the formula: -(CH 2 ) m -, wherein m is an integer from 1 to 3; -C(O)-, -C(CH 3 ) 2 -and-SO 2 -, and it may contain one or more aromatic groups; preferably X-SO 2 -R* Ar , where R* Ar It is C 6 -C 18 A possibly substituted aromatic group; the reaction can give a compound of formula (I) having a group G / G' of the formula -E-Ar-X" as described above, wherein -E- is -SO 2 - groups;

[0085] - Step (C-2): sulfonation, in particular with concentrated sulfuric acid or chlorosulfonic acid, which can give a compound of formula (I) having the formula -SO 2 The group G / G' of Y'; sulfonation reaction, preferably with oleum, concentrated sulfuric acid or Cl-SO 2 -OH, a compound of formula (I) can be obtained, which has the formula -SO 3 H or SO 2Cl, which can be further functionalized to provide compounds of formula (I) having a group G / G' of the formula -E-Ar-X" as detailed above, wherein E = -SO 2 -;

[0086] - Step (C-3): Nitration, in particular with nitronium ions, generated in situ, for example by reaction of concentrated sulfuric acid and nitric acid, which can give compounds of formula (I) having the formula -NO as detailed above 2 The group G / G'; this step may be followed by reduction to generate -NO 2 The steps of converting the above-described compound into a compound of formula (I) can be performed to obtain a compound of formula (I) having the formula -NR H 1 R H 2 The group G / G'.

[0087] When G" is a halogen selected from F, Cl, Br, I, in particular -F, -Cl, step (c) advantageously comprises at least one step selected from the group consisting of:

[0088] - Step (C-4), nucleophilic substitution by reaction of:

[0089] (j) an alkali metal hydroxide (NaOH, KOH, ...) to obtain a compound of formula (I) wherein G / G' is -OH;

[0090] (jj) Compounds containing CN (NaCN, KCN, K 4 [Fe(CN) 6 ] ...), to give the corresponding CN-substituted compound, wherein (jj-1) can be hydrolyzed to provide a compound of formula (I), wherein G / G' is a group of formula -COY as detailed above, or (jj-2) can be reacted with a compound of formula to provide a compound of formula (I), wherein G / G' is a compound of formula A group in which X z Yes-NH 2 ;-NO 2 ; -OH, -X°°, -C(O)X # , where X # is -OH or -X°; wherein X°° is a halogen selected from F, Cl, Br, I, in particular -F, -Cl;

[0091] (jjj) Base (alkyl) amide (KNH 2 、NaNH 2 ...), to obtain a compound of formula (I), wherein G / G' is of the formula -NR H1 R H 2 The group, as described in detail above;

[0092] - Step (C-5): reacting with Mg or Li to form the corresponding organomagnesium or organolithium compound of formula (I), wherein G / G' is of the formula -MgX Mg or -Li group, where X Mg is halogen, preferably Cl or Br, which can be further reacted to form a derivative having formula (I), wherein G / G' is a group of formula -E-Ar-X", as detailed above, wherein X" is hydrogen or halogen, as detailed above, preferably hydrogen.

[0093] When G' is C 1 -C 3 When alkyl is present, step (c) advantageously comprises at least one step selected from the group consisting of:

[0094] - Step (C-6): oxidation, for example in KMnO 4 to provide a compound of formula (I), wherein G / G' is a group of formula -COY, as described above; the group of formula -COY, as described above, can be with a group of formula to provide a compound of formula (I), wherein G / G' is of formula A group in which X z Yes-NH 2 ;-NO 2 ; -OH, -X°°, -C(O)X # , where X # It is -OH or -X°; wherein X°° is a halogen selected from F, Cl, Br, I, especially -F, -Cl.

[0095] When G' is C 1 -C 3 When alkoxy is present, step (c) advantageously comprises at least one step selected from the group consisting of:

[0096] - Step (C-7): hydrolysis, for example in the presence of acetic acid / hydrobromic acid, to provide a compound of formula (I) wherein G / G' is a group of formula -OH.

[0097] Providing the anion of formula (II) can be achieved by reacting the corresponding phenol derivative of formula (IIp) with a base:

[0098]

[0099] wherein n and G" have the same meanings as indicated above.

[0100] Generally, monosubstituted phenols carrying the group G" in the para position will be preferred.

[0101] Any base may be used to extract the acidic protons from the compound of formula (IIp); in particular, alkali metal or alkaline earth metal hydroxides may be used. Although the reaction between the compound of formula (IIp) and the base may be carried out in an aqueous medium, compound (II) is generally provided in step (a) of the process of the invention in a substantially anhydrous form, i.e. in a form comprising a residual water content of less than 500 ppm, preferably less than 200 ppm, even more preferably less than 50 ppm.

[0102] Step (a) is generally carried out in the presence of a polar organic solvent; in particular, ethereal solvents have been found to be particularly effective, being able to adequately dissolve the compound of formula (II) while having sufficient solvation and pK a The properties are favorable for the substitution reaction to produce the corresponding trifluorovinyl ether derivatives, notably -O-CF 2 -CF 2 -H substituted addition reaction or even to form other higher molecular weight derivatives. Among the aliphatic ethers, polar organic solvents that have been found to be particularly effective in step (a) are notably diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, methyl tert-butyl ether, diamyl ether, diisoamyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, diethylene glycol dimethyl ether; dioxane, tetrahydrofuran (THF), of which THF is particularly preferred. Mixtures of one or more of the above solvents can be used.

[0103] In step (a), the reaction temperature is maintained at a temperature of at most 115° C., preferably at most 110° C., even more preferably at most 100° C. The lower limit of the reaction temperature in step (a) is usually adjusted to achieve reasonable reaction kinetics; therefore, a temperature of at least 45° C., preferably at least 55° C., is usually preferred.

[0104] In step (a), the reaction pressure is at least 4 bar, preferably at least 4.5 bar, even more preferably at least 5 bar. For practical reasons, the upper limit of the reaction pressure in step (a) is usually adjusted to less than 30 bar, typically less than 27 bar, even more preferably 25 bar. Typically, in step (a), an excess of gaseous tetrafluoroethylene (TFE) may be added to generate an initial reaction pressure, which is then gradually reduced as the TFE reacts; alternatively, TFE may be subsequently added continuously or stepwise to balance the pressure drop caused by the progress of the TFE conversion. It has been found that maintaining a pressure of more than 4 bar at a substantially constant set point pressure value by adding, preferably continuously adding, TFE is a preferred embodiment for controlling the selectivity of the reaction, and maintaining substantially constant reaction conditions throughout step (a).

[0105] The process of the invention comprises a step (b): dimerizing at least one compound of formula (III) obtained from step (a) by heat treatment at a temperature exceeding 150° C. Usually, in the target compound (I), the groups G and G′ are identical, so step (b) is preferably carried out using only one compound of formula (III) as described in detail above. Nevertheless, the alternative of using a mixture of two different compounds of formula (III) is also included; the resulting dimerization product is therefore a mixture of compounds that produce variable groups G″ and G″′.

[0106] The reaction in step (b) is usually carried out in an inert atmosphere, usually in a nitrogen atmosphere. Pressures exceeding atmospheric pressure, for example, 1.5 bar, preferably 2.0 bar, even more preferably 2.5 bar, may be preferred. The reaction temperature is usually at least 155° C., preferably at least 160° C. Although higher temperatures may be favorable for the kinetics of dimerization, temperatures below 210° C., preferably below 205° C., even more preferably below 200° C. are preferred to minimize side reactions, such as leading to decomposition of the compound.

[0107] As mentioned above, the method of the present invention may or may not include a further step (C).

[0108] According to a first embodiment of the present invention, the compound of formula (II) is a phenolate (ie G"=H), and the process of the present invention comprises a further step (1-C) of reacting G"=H to provide a compound (I), wherein the group G / G' is selected from the groups listed above.

[0109] According to a first variant, the process of the invention comprises reacting in step (a) a compound of formula (II) in which G" is a precursor of G / G' and G"=H, and comprises steps (IV-C) comprising:

[0110] -Step (1V-C-1): Under electrophilic nitration conditions, usually in HNO 3 / H 2 SO 4 In the presence of, reacting a compound of formula (IV) wherein G" = H to obtain a compound of formula (I) wherein G and G' = -NO 2 ;

[0111] - Step (1V-C-2): reacting the compound under reducing conditions, for example in the presence of hydrazine and a Pd / C catalyst, to obtain a compound having formula (I), wherein G and G' are -NH 2 .

[0112] According to a second variant, the process of the invention comprises reacting in step (a) a compound of formula (II) wherein G" is a precursor of G / G' and G" is a halogen chosen from the group consisting of F, Cl, Br, I, in particular -F, -Br, -Cl, and comprises step (2V-C) comprising:

[0113] - Step (2V-C-1): a compound of formula (IV) (wherein G" is a halogen selected from the group consisting of F, Cl, Br, I, in particular -F, -Br, -Cl) and a compound of formula MeNH 2 (wherein Me is a monovalent metal cation) in the presence of ammonia,

[0114] Thus, a compound of formula (I) is obtained, wherein G and G' are -NH 2 .

[0115] Depending on the starting material of formula (II), the compound of formula (I) may be a mixture of positional isomers, wherein G and G'-NH 2 The group is independently located at the ortho, meta or para position on each benzene ring of compound (I).

[0116] According to a third variant, the process of the invention comprises reacting in step (a) a compound of formula (II) in which G" is equal to G / G' and G" is a halogen chosen from the group consisting of F, Cl, Br, I, in particular -F, -Br, -Cl, so as to obtain a compound of formula (I) in which G and G' are halogens chosen from F, Cl, Br, I; the process notably:

[0117] - advantageously does not include any step (C), since the target compound (I) is a compound in which G and G' are halogens; and

[0118] - Preference is given to a process in which n=1 and G / G' / G" is in the para position relative to the oxygen atoms in compounds (I) and (II).

[0119] According to a fourth variant, the process of the invention comprises reacting in step (a) a compound of formula (II) in which G" is a precursor of G / G' and G"=H, and comprises steps (4V-C) comprising:

[0120] - Step (4V-C-1): a compound of formula (IV) wherein G″=H is subjected to an electrophilic sulfonation reaction, notably with concentrated H 2 SO 4 or with a halosulfonic acid to obtain a compound of formula (I) wherein G / G' is a group -SO 2Y', Y' is -OH or -X', X' is a halogen selected from F, Cl, Br, I, especially -F, -Cl;

[0121] -Optional step (4V-C-2): halogenating the compound of formula (IV) to obtain the corresponding compound, wherein the group -SO 2 Y' in Y' is -Br, -Cl or -F;

[0122] - Step (4V-C-3): subjecting the compound of formula (I) thus obtained (wherein G / G' is a group -SO 2 Y') with an aromatic compound of formula Ar-X ° (wherein X ° is hydrogen, or a halogen selected from F, Cl, Br, I, in particular -F, -Cl) to obtain a compound of formula (I), wherein G / G 'is a group of formula -E-Ar-X ", as described in detail above.

[0123] According to a fifth variant, the process of the invention comprises reacting in step (a) a compound of formula (II) in which G" is a precursor of G / G' and G" is a hydrogen atom (G"=H), and comprises steps (5V-C) comprising:

[0124] - Step (5V-C-1): reacting a compound of formula (IV) (wherein G" = H) with XR' hyc Reactants react, where X = Cl, Br, which bind to R' hyc sp of the group 3 -hybridized carbon, and R' hyc It is C 1 -C 18 The hydrocarbon groups which may be substituted include the sp 3 -hybridized carbon, which contains one or more groups of the formula: -(CH 2 ) m -, wherein m is an integer from 1 to 3; and -C(CH 3 ) 2 -, and it contains one or more aromatic groups;

[0125] to obtain compound (I) having a group G / G' of the formula -E-Ar-X" as detailed above.

[0126] According to a sixth variant, the process of the invention comprises reacting in step (a) a compound of formula (II) wherein G" is a precursor of G / G' and G"=H, and comprises steps (6V-C) comprising:

[0127] -Step (6V-C-1): Use XC(O)-R" hycThe reactants react a compound of formula (IV) wherein G" = H with (ii) an acyl group wherein X = Cl, Br, and R" hyc It is C 1 -C 18 A hydrocarbyl group which may be substituted contains one or more groups of the formula: -(CH 2 ) m -, wherein m is an integer from 1 to 3; -C(CH 3 ) 2 -, and -SO 2 -, and it contains one or more aromatic groups;

[0128] To obtain a compound of formula (I) having a group G / G' of the formula -E-Ar-X" as detailed above, wherein -E- is -C(O)-.

[0129] According to a seventh variant, the process of the invention comprises reacting in step (a) a compound of formula (II) wherein G" is a precursor of G / G' and G"=H, and comprises steps (7V-C) comprising:

[0130] - Step (7V-C-1): reacting a compound of formula (IV) (wherein G"=H) with (iii) a compound of formula XS(O) 2 -R'" hyc The sulfonyl halide reactant is reacted with X = Cl, Br, and R'" hyc It is C 1 -C 18 a possibly substituted hydrocarbon radical comprising one or more aromatic groups;

[0131] To obtain a compound of formula (I) having a group G / G' of formula -E-Ar-X" as detailed above, wherein -E- is -S(O) 2 -.

[0132] The present invention further relates to certain novel perfluorocyclobutyl-containing monomers having formula (I) as described in detail above, wherein G and G' are radicals of the formula -E-Ar-X", X" being hydrogen, -OH, -X°, -C(O)X # , X # is -OH or -X°; wherein X°° is a halogen selected from Cl, Br, I, in particular -Cl; -E- is a divalent bridging group selected from the group consisting of: a bond, C 1 -C 6 Exemplary embodiments of a carbon-containing bridging group or a sulfur-containing bridging group; -E- are notably: -(CH 2 ) m -, wherein m is an integer from 1 to 3; -C(O)-, -C(CH3 ) 2 -, and -SO 2 -; -Ar- is a divalent aromatic group, in particular (optionally substituted) phenyl (-Ph-), for example, wherein the connecting bonds in -Ph- may be in the ortho-, meta- or para-position relative to each other, preferably in the para-position.

[0133] In addition, the present invention relates to a method for preparing a polycondensation polymer, the method comprising:

[0134] - preparing a compound of formula (I) according to the process detailed above; and

[0135] - polycondensing it with at least one further compound having at least two reactive groups which are capable of reacting by a condensation reaction with the groups G and G' of the compound of formula (I).

[0136] According to certain embodiments, the polycondensation polymer is a polymer selected from the group consisting of polyimide, polyamide and polyamideimide, and the compound of formula (I) is wherein G and G' are of formula -NH 2 According to this embodiment, the compound having formula (I) can be polycondensed with a polycarboxylic acid selected from the group consisting of:

[0137] - dicarboxylic acids (or their derivatives), usually forming polyamide polymers;

[0138] a polycarboxylic acid comprising at least two alpha, beta or ortho carboxylic acid groups (or derivatives thereof, particularly in the form of anhydrides thereof) and at least one further carboxylic acid group (or derivatives thereof), typically forming a polyamideimide polymer; and

[0139] - polycarboxylic acids containing two pairs of alpha, beta or ortho carboxylic acid groups (or their derivatives, especially in the form of their anhydrides), usually forming polyimide polymers.

[0140] It is further understood that further diamino compounds may be used to form copolymers of compounds of formula (I) with other units derived from perfluorocyclobutyl; the relative amount of units derived from compounds of formula (I) may represent at least 1%, preferably at least 2%, more preferably at least 5% by mole, relative to the total moles of repeating units of the copolymer of compounds of formula (I); and / or at most 50%, preferably at most 30%, more preferably at most 20%, even more preferably at most 15%, by mole.

[0141] Should the disclosure of any patents, patent applications, and publications incorporated herein by reference conflict with the description of the present application to the extent that it renders a term unclear, the present description shall take precedence.

[0142] The present invention will now be described in more detail with reference to the following examples, which are for illustrative purposes only and are not intended to limit the scope of the present invention.

[0143] Preparation Example 1:

[0144]

[0145] Steps (a) and (b): Ph-O-CF=CF 2 Synthesis of (TFVOB-H) and Dimerization to Ph-OC 4 F 6 -O-Ph(DPhFCB-H)

[0146] A 50 g sample of phenol was charged into a glass flask together with 210 g of a 10% wt aqueous NaOH solution. The solution was stirred for 25 minutes and then the water was completely removed using a rotary evaporator to obtain a dry white powder of sodium phenolate. 390 g of THF was used to dissolve the sodium phenolate. The obtained solution was transferred to a 600 mL stainless steel autoclave and, after purging with nitrogen and an ultimate vacuum of 0.3 bar, maintained at 65 ° C at 10 bar C. 2 F 4 Stir for 6 hours at constant pressure. The obtained solution is transferred to a separatory funnel and washed with 1800 ml of distilled water. The organic phase is separated and distilled under vacuum from 155 mbar to 2 mbar to obtain 64 g of a colorless liquid, which is characterized by F19 and H1 NMR and determined to be trifluorovinylhydroxybenzene (TFVOB-H) with a purity of 96%. The overall molar yield is 66%.

[0147] Step (b): Dimerization to Ph-OC 4 F 6 -O-Ph(DPhFCB-H)

[0148] The obtained TFVOB-H was transferred to a stainless steel tank, pressurized with 3 bar of nitrogen and heated at 180°C for 42 hours.

[0149] The pot was then cooled, and the obtained product was recovered and vacuum distilled at 2 mbar to obtain 59 g of a product characterized by 19F-NMR and 1H-NMR and identified as [(hexafluorocyclobutanediyl)bis(oxy)]diphenyl (DPhFCB-H) with a purity of 99.2%.

[0150] Step (c):

[0151] (C-1): O 2 N-Ph-OC 4 F 6 -O-Ph-NO 2 (DPhFCB-NO 2)

[0152] To a well-stirred solution of DPhFCB-1 (50 g, 0.144 mol) in DCM (250 mL) was added a mixed acid, namely HNO, dropwise via a dropping funnel at 0 °C over a period of 45 min. 3 (46g) and H 2 SO 4 The mixture of 138g was added. After the acid mixture was fully added, the reaction mass was stirred for another 1.5 hours at 20°C. After the reaction was completed, it was diluted with ice-cold water (1 liter) and neutralized with sodium bicarbonate. The compound was extracted with ethyl acetate (400mL x 3). The organic layer was dried over sodium sulfate and concentrated by rotary evaporation. The pure compound DPhFCB-NO was isolated after crystallization from ethyl acetate. 2 , as white crystals (yield 70%, 44 g), purity>98% (GC).

[0153] (C-2): H 2 N-Ph-OC 4 F 6 -O-Ph-NH 2 Synthesis

[0154] DPhFCB-NO 2 10% Pd / C (0.575 g) was added to a well-stirred solution of (20 g, 0.045 mol) in MeOH (250 mL). A dropping funnel was used to add a hydrazine hydrate solution (80%, 21.56 mL) over a period of 1 hour. After the reagent addition was complete, the reaction mixture was refluxed for another 1.5 hours. The solution was then cooled to room temperature and filtered through diatomaceous earth. The filtrate was evaporated to remove MeOH. The obtained resin mass was dissolved in DCM and washed with water to remove excess hydrazine hydrate. The organic layer was dried over sodium sulfate and evaporated to dryness. The final product DPhFCB-NH 2 It is a colorless colloidal liquid (yield 85%, 14.8 g) with a purity of 98% (HPLC).

[0155] Preparation Example 2

[0156] Step (a): 40.04 g of 4-bromophenol sample was placed in a glass flask along with 109 g of a 10% wt aqueous NaOH solution. The solution was stirred for 25 minutes and then completely dehydrated using a rotary evaporator to obtain 4-bromo-sodium phenolate as a pale yellow powder. 282 g of THF was used to dissolve the 4-bromo-sodium phenolate. The obtained solution was transferred to a 600 mL stainless steel autoclave and, after purging with nitrogen and applying a limiting vacuum of 0.3 bar, maintained at 65 ° C at 10 bar C. 2 F 4Stir for 6 hours at constant pressure. The obtained solution is transferred to a separatory funnel and washed with 1800 ml of distilled water. The organic phase is separated and vacuum distilled from 17 mbar to 1 mbar to obtain 43 g of a colorless liquid, which is characterized by NMR F19 and H1 and identified as trifluoroethyleneoxy-4-bromo-benzene (TFVOB-Br) with a purity of 87%. The molar yield is 63%.

[0157] Step (b): The obtained TFVOB-Br was transferred to a stainless steel tank, pressurized with 3 bar of nitrogen and heated at 180°C for 42 hours.

[0158] The pot was then cooled, the product obtained was recovered and vacuum distilled at 0.27 mbar to obtain 28 g of the final product, which was 19 F-NMR and 1 The product was characterized by H-NMR and determined to be [(hexafluorocyclobutanediyl)bis(oxy)]diphenyl bromide (DPhFCB-Br) with a purity of 99.5%.

[0159] Preparation Example 3

[0160] Steps (a) and (b): See Preparation Example 2.

[0161] Step (c1): NC-Ph-OC 4 F 6 Synthesis of -O-Ph-CN(DPhFCB-CN)

[0162] To a well-stirred solution of DPhFCB-Br (3 g, 5.92 mmol) in NMP (10 mL) was added K 4 Fe(CN) 6 (dry) (1.09 g, 2.96 mmol), Na 2 CO 3 (1.25 g, 11.79 mmol), Pd(OAc) 2 (0.265 g, 1.18 mmol). The reaction mass was then stirred for another 24 hours at 120 ° C under nitrogen. After the reaction was completed, it was diluted with water (100 mL). The compound was extracted with ethyl acetate (50 mL x 3). The organic layer was dried over sodium sulfate and concentrated by rotary evaporation. After column chromatography, the pure compound was isolated as a colorless liquid (yield 80%).

[0163] Step (c2): HOOC-Ph-OC 4 F 6 Synthesis of -O-Ph-COOH(DPhFCB-COOH)

[0164] DPhFCB-CN (2 g, 5.05 mol) was added ton KOH (2.8 g, 44.6 mol) was added to the well-stirred solution in BuOH (6 mL). The reaction mixture was refluxed for 4 hours. The solution was then cooled to room temperature and diluted with water (10 mL). The solution was then acidified with dilute HCl. The precipitate was filtered and washed 4 times with water (10 mL) to remove traces of mineral acid. The desired product was isolated as a white solid (yield 60%).

[0165] Polymerization Example 4: DPhFCB-NH 2 Synthesis of polyimide with pyromellitic acid

[0166] A double-walled round-bottom flask with a temperature controller was charged with 0.658 g (2.59 mmol) of 98% pyromellitic acid and 5.5 mL of pure methanol. The reaction medium was stirred and heated to 50° C. while being gently flushed with nitrogen. In a 50 mL round-bottom flask, 1.0 g (2.645 mmol) of 98% DPhFCB-NH 2 Dissolve in 8.5 mL of pure methanol. The solution is then placed in a dropping funnel connected to a double-walled round-bottom flask and added dropwise to the methanol solution of pyromellitic acid over 15 minutes. The reaction medium is kept under nitrogen at 50°C with vigorous stirring for 1 hour and 30 minutes. The temperature is then lowered to 25°C and stirred for another 30 minutes to ease further precipitation. The salt powder is recovered by filtration on a Buchner funnel and washed 3 times with ice-cold methanol to remove unreacted raw materials. The salt is then ground and dried in vacuo at 60°C overnight. The melting temperature of the salt is 240°C.

[0167] DPhFCB-NH 2 -PMA salt powder was placed in a flask attached to a Kugelrohr and rotated (rpm 30) under gentle flushing with nitrogen. The flask was heated and rotated at 220°C for 2 hours and at 240°C for 1 hour. The obtained PI powder was found to be yellow. TGA analysis showed a weight loss of 5% at a temperature of 506°C. FTIR analysis of the polyimide powder showed characteristic absorption bands of the imide functional group at 1390, 1720 and 1783 cm -1 and the absence of characteristic absorption bands of amine functional groups was noted.

[0168] Polymerization Example 5: DPhFCB-NH 2 Synthesis of polyimide with biphenyltetracarboxylic acid (BPTA)

[0169] A double-walled round-bottom flask with a temperature controller was charged with 0.856 g (2.59 mmol) of 98% biphenyltetracarboxylic acid (BPTA) and 12.6 mL of pure methanol. The reaction medium was stirred and heated to 50° C. while being gently flushed with nitrogen. In a 50 mL round-bottom flask, 1.0 g (2.645 mmol) of 98% DPhFCB-NH 2 Dissolved in 12.6 mL of pure methanol. The solution was then placed in a dropping funnel connected to a double-walled round-bottom flask and added dropwise to the methanol solution of BPTA over 15 minutes. The reaction medium was kept under nitrogen at 50 ° C with vigorous stirring for 1 hour and 30 minutes. The temperature was then reduced to 25 ° C and stirred for another 30 minutes to alleviate further precipitation. The salt powder was recovered by filtration on a Buchner funnel and washed 3 times with ice-cold methanol to remove unreacted starting materials. The salt was then ground and dried in vacuo at 60 ° C overnight. The melting temperature of the salt was found to be 228 ° C.

[0170] DPhFCB-NH 2 -BPTA salt powder was placed in a flask attached to a Kugelrohr and rotated (rpm 30) under gentle flushing with nitrogen. The pressure was equal to atmospheric pressure. The flask was then heated at 200°C and rotated for 9 hours. The PI powder obtained was found to be yellow. TGA analysis showed a weight loss of 5% at a temperature of 496°C. FTIR analysis of the PI powder showed characteristic absorption bands of the imide functional group at 1375, 1719 and 1777 cm -1 The DSC showed a melt at 348°C (melting enthalpy of 36.2 J / g) and a glass transition temperature of 225°C.

[0171] Polymerization Example 6: From DPhFCB-NH 2 Synthesis of polyimide with 4,4'-(hexafluoroisopropylidene)diphthalic anhydride (6-FDA)

[0172] In a typical polymerization, a three-necked round-bottom flask equipped with a magnetic stirrer, nitrogen inlet / outlet, and DPhFCB-NH 2(0.851g, 2.25mmol) and N-methyl-2-pyrrolidone (NMP) (16mL). 4,4'-(hexafluoroisopropylidene) diphthalic anhydride (6-FDA) (1.0g, 2.25mmol) was added to the stirred solution in batches, and the resulting solution was stirred at room temperature for 24 hours under an inert atmosphere. The obtained poly (amic acid) solution was poured into a flat PTFE culture dish and heated at 70°C for 24 hours in a vacuum oven, then at 100-275°C (temperature ramp: 25°C / 1.0 hour) and finally at 300°C for 1.0 hour to obtain a transparent film. TGA analysis showed a weight loss of 5% at a temperature of 496°C. FTIR analysis of the polyimide film showed that the imide functional groups were at 1375, 1719 and 1777cm -1 The characteristic absorption band at . DSC shows that the glass transition temperature is 246℃.

Claims

1. A method for preparing a compound having the general formula (I): wherein each G and G', being the same or different from each other, are independently selected from the group consisting of - halogen selected from F, Cl, Br, I; --NR H 1 R H 2 , where R H 1 and R H 2 are independently H or C1-C6 hydrocarbon; --OH; - a nitrile group of the formula -CN and a nitro group of the formula -NO2; --COY, wherein Y is -X, X is a halogen selected from F, Cl, Br, I; -OH; -OR H 3 、-NR H 1 R H 2 , where R H 3 It is C1-C 12 A hydrocarbon group; and R H 1 and R H 2 has the meaning detailed above; --SO2Y', wherein Y' is -OH or -X', and X' is a halogen selected from F, Cl, Br, I; --E-Ar-X", where X" is hydrogen, -OH, -X°°, -C(O)X # , where X # is -OH or -X°; wherein X°° is a halogen selected from F, Cl, Br, I; -E- is a divalent bridging group selected from the group consisting of: a bond, a C1-C6 carbon-containing bridging group; a sulfur-containing bridging group; -Ar- is a divalent aromatic group, - a group having the formula Where X z -NH2; -NO2; -OH, -X°°, -C(O)X # , where X # is -OH or -X°; wherein X°° is a halogen selected from F, Cl, Br, I; - Each n, the same or different from each other, is an integer from 1 to 3 The method comprises: Step (a): making an anion having the formula (II): wherein G" is a group G or G' as described above, or a precursor thereof, reacted with tetrafluoroethylene at a temperature of up to 115°C and a pressure of at least 4 bar, to obtain a compound of formula (III): Step (b): a step of dimerizing at least one compound of formula (III) obtained from step (a) by heat treatment at a temperature exceeding 150° C. to obtain a compound of formula (IV): wherein G" and G"' are each a group G or G' as described above, or a precursor thereof, it being understood that when G" and G"' are a group G or G' as described above, the compound of formula (IV) meets the requirements of the compound of formula (I); as well as Step (c): Optionally, a step of reacting a compound of formula (IV) under appropriate conditions to convert the precursor groups G" and G"' of formula (IV) into groups G and G' to obtain the above compound of formula (I).

2. The method of claim 1, wherein: All halogens are -F or -Cl.

3. The method of claim 1, wherein: The R H 1 and R H 2 It's H.

4. The method of claim 1, wherein: The R H 3 It is C1-C6 alkyl or C6-C 12 Aryl.

5. The method of claim 1, wherein: Said Y is OH.

6. The method of claim 1, wherein: The -E- is -(CH2) m -, wherein m is an integer from 1 to 3; -C(O)-, -C(CH3)2-, and -SO2-.

7. The method of claim 1, wherein: The -Ar- is optionally substituted phenyl-Ph-.

8. The method of claim 7, wherein: The connecting bonds in the -Ph- are in the ortho, meta or para position relative to each other.

9. The method of claim 8, wherein: The connecting key is in alignment.

10. The method of claim 1, wherein: The n is an integer of 1 to 2.

11. The method of claim 1, wherein: Said n=1.

12. The method of claim 1, wherein: Providing the anion of formula (II) is achieved by reacting the corresponding phenol derivative of formula (IIp) with a base: wherein n and G" have the meanings as indicated in claim 1, and wherein the base is selected from hydroxides of alkali metals or alkaline earth metals.

13. The method according to claim 1 or 12, wherein: Compound (II) is provided in step (a) in a substantially anhydrous form, ie in a form comprising a residual water content of less than 500 ppm.

14. The method of claim 13, wherein the residual water content is less than 200 ppm.

15. The method of claim 13, wherein the residual water content is less than 50 ppm.

16. The method of claim 1 or 12, wherein: Step (a) is carried out in the presence of a polar organic solvent.

17. The method of claim 16, wherein the solvent is selected from the group consisting of aliphatic ethers, dioxane, tetrahydrofuran (THF).

18. The method of claim 17, wherein the aliphatic ether is selected from ethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, methyl tert-butyl ether, diamyl ether, diisoamyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, diethylene glycol dimethyl ether.

19. The method of claim 16, wherein: In step (a), the reaction temperature is maintained at a temperature of at most 115°C, and / or at least 45°C; and / or wherein in step (a), the reaction pressure is at least 4 bar, and / or at most 30 bar.

20. The method of claim 19, wherein the temperature is at most 110°C.

21. The method of claim 19, wherein the temperature is at most 100°C.

22. The method of claim 19, wherein the temperature is at least 55°C.

23. The process of claim 19, wherein the reaction pressure is at least 4.5 bar.

24. The process of claim 19, wherein the reaction pressure is at least 5 bar.

25. The process of claim 19, wherein the reaction pressure is below 27 bar.

26. The process of claim 19, wherein the reaction pressure is below 25 bar.

27. The method of claim 1 or 12, wherein: Step (b) is carried out using only one compound of formula (III), and / or wherein the reaction in step (b) is carried out in an inert atmosphere, at a pressure exceeding atmospheric pressure and / or at a reaction temperature of at least 155°C and / or below 210°C.

28. The method of claim 27, wherein the inert atmosphere is a nitrogen atmosphere.

29. The method of claim 27, wherein the temperature is at least 160°C.

30. The method of claim 27, wherein the temperature is less than 205°C.

31. The method of claim 27, wherein the temperature is less than 200°C.

32. The method of claim 1 or 12, wherein: G" in formula (III) is a group G or G', and the process of the present invention obtains the target product having formula (I) by the sequence of steps (a) and (b).

33. The method of claim 32, wherein G" is a halogen selected from the group consisting of F, Cl, Br, I.

34. The method of claim 1 or 12, wherein: G" in formula (III) is different from the groups G and G'.

35. The method of claim 34, wherein G" is selected from the group consisting of: -hydrogen; - halogen selected from F, Cl, Br, I; -C1-C3 alkyl; -C1-C3 alkoxy.

36. The method of claim 35, wherein the alkyl group is methyl -CH3.

37. The method of claim 35, wherein the alkoxy group is of the formula -OR alk A group in which R alk It is a C1-C3 alkyl group.

38. The method of claim 37, wherein the alkoxy group is a group of formula -OCH3.

39. The method of claim 34, wherein: G" is hydrogen, and step (c) comprises at least one step selected from the group consisting of: - Step (C-1): electrophilic aromatic substitution, wherein the hydrogen G" atom reacts with an electrophilic reagent selected from the group consisting of: (i)XR' hyc Reactants, where X = Cl, Br, which bind to R' hyc sp of the group 3 -hybridized carbon, and R' hyc Is the sp 3 - Hybridized carbon C1-C 18 Hydrocarbon; (ii) XC(O)-R” hyc Reactants, where X = Cl, Br, and R" hyc It is C1-C 18 Hydrocarbon; (iii)X-SO2-R * hyc Reactants, where X = Cl, Br, and R * hyc It is C1-C 18 Hydrocarbon; - step (C-2): sulfonation, which gives a compound of formula (I) having a group G / G' of formula -SO2Y' as detailed in claim 1; - Step (C-3): Nitration to obtain a compound of formula (I) having the formula -NR H 1 R H 2 The group G / G'.

40. The method of claim 39, wherein the hydrogen G" atom is reacted with an electrophile in the presence of a Lewis acid.

41. The method of claim 39, wherein the C1-C 18 The hydrocarbon group is substituted.

42. The method of claim 39, wherein X-SO2-R * hyc The reactants are X-SO2-R* Ar , where X = Cl, Br and where R* Ar It is C6-C 18 Aromatic groups.

43. The method of claim 42, wherein the C6-C 18 The aromatic group is substituted.

44. The method of claim 39, wherein the sulfonation is carried out with concentrated sulfuric acid or chlorosulfonic acid.

45. The method of claim 39, wherein the nitration is with a nitronium ion.

46. ​​The method of claim 45, wherein the nitronium ion is generated in situ by the reaction of concentrated sulfuric acid and nitric acid.

47. The method of claim 39, wherein step (C-3) is followed by a reduction step.

48. The method of claim 39, wherein the C1-C 18 The hydrocarbon group contains one or more groups having the formula: -(CH2) m -, wherein m is an integer from 1 to 3; -C(O)-, -C(CH3)2- and -SO2-.

49. The method of claim 39, wherein the C1-C 18 The hydrocarbyl group contains one or more aromatic groups.

50. The method of claim 34, wherein: G" is a halogen selected from F, Cl, Br, I, and wherein step (c) comprises at least one step selected from the group consisting of: - Step (C-4), nucleophilic substitution by reaction of: (j) an alkali metal hydroxide to obtain a compound of formula (I) wherein G / G' is -OH; (jj) a compound containing CN to give the corresponding CN-substituted compound, which is hydrolyzed to provide a compound of formula (I) wherein G / G' is a group of formula -COY as detailed in claim 1, or which is reacted with an o-aminophenol derivative of the formula To provide a compound of formula (I), wherein G / G' is a group having the formula Where X z -NH2; -NO2; -OH, -X°°, -C(O)X # , where X # is -OH or -X°; wherein X°° is a halogen selected from F, Cl, Br, I; (jjj) an alkali metal amide or an alkali metal alkyl amide to obtain a compound of formula (I), wherein G / G' is a compound of formula -NR H 1 R H 2 Groups; - Step (C-5): reacting with Mg or Li to form the corresponding organomagnesium or organolithium compound of formula (I), wherein G / G' is of the formula -MgX Mg or -Li group, where X Mg is halogen, which is further reacted to form a derivative having formula (I), wherein G / G' is a group of formula -E-Ar-X" as detailed in claim 1, wherein X" is hydrogen or halogen.

51. The method of claim 50, wherein the alkali metal hydroxide is NaOH, KOH.

52. The method of claim 50, wherein the compound comprising CN is NaCN, KCN, K4[Fe(CN)6].

53. The method of claim 50, wherein the alkali metal amide is KNH2, NaNH2.

54. The method of claim 50, wherein X Mg It is Cl or Br.

55. The method of claim 34, wherein: G" is C1-C3 alkyl, and wherein step (c) comprises at least one step selected from the group consisting of: - Step (C-6): oxidation to provide a compound having formula (I), wherein G / G' is a group of formula -COY as detailed in claim 1, wherein the group of formula -COY is reacted with an o-aminophenol derivative having the formula To provide a compound of formula (I), wherein G / G' is a group having the formula Where X z -NH2; -NO2; -OH, -X°°, -C(O)X # , where X # is -OH or -X°; wherein X°° is a halogen selected from F, Cl, Br, I.

56. The method of claim 55, wherein the oxidation is performed in the presence of KMnO4.

57. The method of claim 34, wherein: G" is C1-C3 alkoxy, and wherein step (c) comprises at least one step selected from the group consisting of: - Step (C-7): hydrolysis to provide a compound of formula (I) wherein G / G' is a group of formula -OH.

58. A method for preparing a polycondensation polymer, the method comprising: - Preparation of a compound of formula (I) according to any one of claims 1 to 57; as well as - polycondensing it with at least one further compound having at least two reactive groups which are capable of reacting by a condensation reaction with the groups G and G' of the compound of formula (I).

59. The method of claim 58, wherein the polycondensation polymer is a polymer selected from the group consisting of polyimide, polyamide and polyamideimide, and the compound having formula (I) is a compound wherein G and G' are groups of formula -NH2.

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