Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
  • C07B39/00—Halogenation
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C17/00—Preparation of halogenated hydrocarbons
  • C07C17/093—Preparation of halogenated hydrocarbons by replacement by halogens
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C25/00—Compounds containing at least one halogen atom bound to a six-membered aromatic ring
  • C07C25/02—Monocyclic aromatic halogenated hydrocarbons
  • C07C25/13—Monocyclic aromatic halogenated hydrocarbons containing fluorine
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
  • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
  • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
  • C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
  • C07D213/61—Halogen atoms or nitro radicals
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D215/00—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems
  • C07D215/02—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom
  • C07D215/16—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
  • C07D215/18—Halogen atoms or nitro radicals
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D215/00—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems
  • C07D215/02—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom
  • C07D215/16—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
  • C07D215/20—Oxygen atoms

Definitions

• the subject of the present invention is a process for preparing fluorinated aromatic compounds from corresponding amines by replacing the amino group with a fluorine atom.
• the brominated or chlorinated aromatic compounds are easily obtained by electrophilic halogenation with bromine or molecular chlorine but the fluoroaromatic compounds are, for their part, much more rarely synthesized directly by fluorination with fluorine; this reaction being difficult to control.
• Two methods of introducing fluorine have been developed. The first consists in replacing a halogen atom by a fluoride by means of the process of exchange of chlorine halogens by fluorine [B. Langlois, L. Gilbert and G. Forât ,, Ind. Chem. Libr., 1996, 8, 244]. This exchange is well suited to chlorinated substrates (or bromines) for which electro-attracting groups are located ortho and / or para halogen.
• groups such as N0 2 can be displaced (fluorodenitration).
• the second method is to replace a diazonium N 2 + group with a fluorine. It is generally carried out in two stages: a diazotization reaction followed by a fluoro-dediazotization.
• an aniline can be diazotized with sodium nitrite in anhydrous hydrofluoric acid and the arenediazonium fluoride thus obtained undergoes thermal decomposition into fluoroaromatics.
• This reaction is used for simple fluoroaromatics (fluorobenzene, 3-fluorotoluene) [N. Ishikawa, Petrotech, 1987, 10, 543].
• the arenediazonium chloride formed is soluble in the medium but the addition of an aqueous solution of sodium tetrafluoroborate or fluoroboric acid causes precipitation of a diazonium tetrafluoroborate formed.
• the aromatic amines can also be diazotized directly in aqueous tetrafluoroboric acid or in aqueous hydrofluoric acid into which boron trifluoride is introduced.
• the arenediazonium tetrafluoroborate obtained undergoes a fluorodediazotization operation by heating until its decomposition into fluoroaromatic compound, nitrogen and boron trifluoride.
• this so-called "Balz and Schiemann" reaction is strongly exothermic.
• the object of the present invention is to provide a method enabling the abovementioned drawbacks to be overcome.
• the term “decomposition temperature of the diazonium salt” means the temperature of transformation of the diazonium salt into the fluoroaromatic compound determined by differential thermal analysis on a previously prepared sample.
• the process of the invention allows direct access to the fluoroaromatic compound, by decomposition of the diazonium salt, without intermediate separation of the latter.
• the process consists in carrying out the decomposition of the diazonium salt formed in the reaction medium, as and when it is formed. The method of the invention thus makes it possible to avoid the safety problems linked to the handling of a diazonium salt.
• the process for the preparation of a fluoroaromatic compound according to the invention comprises the following sequences: - mixing by introduction, in any order, the source of boron trifluoride, the aromatic compound carrying at least at least one amino group on the aromatic cycle and the organic solvent, - the reaction medium is brought to the decomposition temperature of the diazonium salt, - the nitrosating agent is gradually added, - the fluoroaromatic compound formed is recovered.
• Another embodiment consists in introducing the reagents in a different order.
• the source of boron trifluoride, the nitrosating agent and the organic solvent are mixed by introduction, in any order; the reaction medium is brought to the decomposition temperature of the diazonium salt; the aromatic compound carrying at least one amino group is gradually added over the aromatic cycle, then the fluoroaromatic compound formed is recovered.
• the process of the invention makes it possible to avoid the accumulation of the diazonium salt in the reaction medium.
• a diazonium salt is prepared intermediately, by reaction of an aromatic compound carrying at least one amino group on the aromatic ring and a nitrosating agent, in the presence of a source of trifluoride. boron, in an organic medium and said diazonium salt is decomposed without intermediate separation.
• aminoaromatic compound means an aromatic compound in which a hydrogen atom directly linked to the aromatic nucleus is replaced respectively by an amino group and by "aromatic compound", the classic notion of aromaticity as defined in the literature, in particular by Jerry MARCH, Advanced Organic Chemistry, 4 th edition, John Wiley and Sons, 1992, pp. 40 and following.
• the invention relates more particularly to the aminoaromatic compounds corresponding to the general formula:
• - A symbolizes the remainder of a cycle forming all or part of a carbocyclic or heterocyclic, aromatic, monocyclic or polycyclic system
• - R identical or different, represent substituents on the cycle
• - m represents the number of substituents on the cycle.
• the invention applies in particular to aminoaromatic compounds corresponding to formula (I) in which A is the residue of a cyclic compound, preferably having at least 4 atoms in the ring, preferably 5 or 6, optionally substituted , and representing at least one of the following cycles:. an aromatic, monocyclic or polycyclic carbocycle,. an aromatic, monocyclic or polycyclic heterocycle comprising at least one of the heteroatoms O, N and S.
• residue A optionally substituted represents, the remainder: 1 ° - of a aromatic, monocyclic or polycyclic carbocyclic compound.
• polycyclic carbocyclic compound is meant:. a compound consisting of at least 2 aromatic carbocycles and forming between them ortho- or ortho- and pericondensed systems,. a compound consisting of at least 2 carbocycles of which only one of them is aromatic and forming between them ortho- or ortho- and pericondensed systems. 2 ° - of an aromatic, monocyclic or polycyclic heterocyclic compound.
• polycyclic heterocyclic compound we define:.
• a compound consisting of at least 2 heterocycles containing at least one heteroatom in each cycle of which at least one of the two cycles is aromatic and forming between them ortho- or ortho- and pericondensed systems a compound consisting of at least one carbocycle and at least one heterocycle of which at least one of the cycles is aromatic and forming between them ortho- or ortho- and pericondensed systems, 3 ° - of a compound constituted by a chain of cycles , as defined in paragraphs 1 and / or 2 linked together:. by a valential link,. by an alkylene or alkylidene group having from 1 to 4 carbon atoms, preferably a methylene or isopropylidene group,.
• R 0 represents a hydrogen atom or an alkyl group having from 1 to 4 carbon atoms , a cyclohexyl or phenyl group.
• the residue A optionally substituted, represents one of the following cycles: - an aromatic carbocycle: an aromatic bicycle comprising two aromatic carbocycles
• a tricycle comprising at least one carbocycle or an aromatic heterocycle
• an aminoaromatic compound of formula (I) in which A represents an aromatic ring, preferably a benzenic, naphthalene, pyridine or quinoleic ring.
• the aromatic compound of formula (I) can carry one or more substituents. The number of substituents present on the cycle depends on the carbon condensation of the cycle and on the presence or not of unsaturations on the cycle.
• the maximum number of substituents likely to be carried by a cycle is easily determined by a person skilled in the art.
• the term "several” is generally understood to mean less than 4 substituents on an aromatic ring. Examples of substituents are given below, but this list is not limiting.
• the group or groups R which are identical or different, preferably represent one of the following groups:. an alkyl group, linear or branched, having from 1 to 6 carbon atoms, preferably from 1 to 4 carbon atoms, such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, .
• an alkenyl or alkynyl group linear or branched having from 2 to 6 carbon atoms, preferably from 2 to 4 carbon atoms, such as vinyl, allyl,. a linear or branched alkoxy group having from 1 to 6 carbon atoms, preferably from 1 to 4 carbon atoms such as methoxy, ethoxy, propoxy, isopropoxy, butoxy groups, an alkenyloxy group, preferably an allyloxy group or a phenoxy group,. a cyclohexyl, phenyl or benzyl group,. an acyl group having from 2 to 6 carbon atoms,.
• Ri represents a valential bond or a divalent hydrocarbon group, linear or branched, saturated or unsaturated, having from 1 to 6 carbon atoms such as, for example, methylene, ethylene, propylene, isopropylene, isopropylidene; the identical or different R 2 groups represent a hydrogen atom or a linear or branched alkyl group having from 1 to
• the present invention applies very particularly to the compounds corresponding to formula (I) in which the group or groups R represent: . an alkyl group, linear or branched, having from 1 to 6 carbon atoms, preferably from 1 to 4 carbon atoms, such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl,. a linear or branched alkenyl group having from 2 to 6 carbon atoms, preferably from 2 to 4 carbon atoms, such as vinyl, allyl,.
• a linear or branched alkoxy group having from 1 to 6 carbon atoms, preferably from 1 to 4 carbon atoms such as methoxy, ethoxy, propoxy, isopropoxy, butoxy groups, an alkenyloxy group, preferably an allyloxy group or a phenoxy group,.
• Ri represents a valence bond or a divalent, linear or branched, saturated or unsaturated hydrocarbon group having from 1 to 6 carbon atoms such as, for example, methylene, ethylene, propylene, isopropylene, isopropylidene; the groups R 2 , which may be identical or different, represent a hydrogen atom or a linear or branched alkyl group having from 1 to 6 carbon atoms or phenyl; M represents a hydrogen atom or a sodium atom.
• m is a number less than or equal to 4, preferably equal to 1 or 2.
• p it is preferably equal to 1 or 2.
• the invention relates more particularly to carbocyclic aromatic compounds of the formula
• the invention preferably relates to nitrogen heterocyclics corresponding to the following formula (Ib):
• - R and m have the meaning given above
• - B represents the remainder of an aromatic, monocyclic heterocycle comprising 5 or 6 atoms of which one or two of them are atoms nitrogen or the remainder of a polycyclic heterocycle comprising on the one hand an aromatic heterocyclic comprising 5 or 6 atoms of which one or two of them are nitrogen atoms and on the other hand a carbocycle or a nitrogen heterocycle, saturated unsaturated or aromatic comprising 5 or 6 atoms.
• any NO + generating nitrosating agent> free of protons is used.
• nitrogen dioxide NO2 nitrogen anhydride N 2 0 3 , nitrogen peroxide N2O4. If the reagent is gaseous under the reaction conditions, it is bubbled through the medium.
• R a represents a linear or branched alkyl group having 1 to 12 carbon atoms, preferably 1 to 6 carbon atoms or a cycloalkyl group having 5 or 6 carbon atoms.
• the n-butyl, tert-butyl or isoamyl nitrite is advantageously chosen.
• boron trifluoride BF 3 can be used in gaseous form. However, it is preferred to use boron trifluoride complexes comprising approximately between 20 and 70% by weight of boron trifluoride.
• complexes comprising boron trifluoride combined with an organic compound of the Lewis base type chosen from water, ethers, alcohols and phenols, acetic acid, acetonitrile .
• organic compound of the Lewis base type chosen from water, ethers, alcohols and phenols, acetic acid, acetonitrile .
• ethers mention may in particular be made of dimethyl ether, diethyl ether, dibutyl ether, methyl-tert-butyl ether.
• alcohols such as methanol, propanol or phenol.
• sources of boron trifluoride which are commercially available are used.
• the boron trifluoride associated with water, acetic acid or diethyl ether is preferably chosen.
• the reaction is carried out in an organic medium, which means that there is the presence of an organic solvent or optionally a mixture of organic solvents.
• the choice of solvent is such that it must not have a reducing character compared to the diazonium salt.
• An aprotic, polar or apolar solvent is used.
• solvents suitable for the process of the invention mention may be made of: - aliphatic hydrocarbons and more particularly paraffins such as, in particular, pentane, hexane, heptane, octane, isooctane, nonane, decane, undecane, tetradecane, petroleum ether and cyclohexane; aromatic hydrocarbons such as, in particular, benzene, toluene, xylenes, ethylbenzene, diethylbenzenes, trimethylbenzenes, cumene, pseudocumene, petroleum fractions consisting of a mixture of alkylbenzenes, in particular cuts of the Solvesso® type, - hydrocarbons aliphatic or aromatic halogens, and we can mention: perchlorinated hydrocarbons such as in particular trichloromethane, tetrachlorethylene; partially chlorinated hydrocarbons such
• chlorobenzene 1,2-dichlorobenzene, toluene and benzonitrile are preferred.
• quantities of reagents and the conditions for carrying out the process of the invention those which are preferred are specified below.
• the amount of diazotization reagent used can vary widely. When it is expressed by the molar ratio aminoaromatic compound / nitrosating agent defined in NO + , it is at least equal to the stoichiometric amount but it is preferable that it is used in an excess which can reach 120% of the amount stoichiometric, and preferably between 100% and 120%.
• the amount of fluoride source used is such that the aminoaromatic compound FV molar ratio varies between 1 and 2, preferably between 1, 2 and 1, 5.
• the concentration of the aminoaromatic substrate in the reaction medium is preferably between 0.5 and 2.5 mol / l and is preferably around 1 mol / l.
• the process of the invention uses a source of nonionic boron trifluoride.
• the temperature and pressure conditions they are advantageously as described below.
• the diazotization reaction of the first step is generally carried out at low temperature, advantageously lying between -10 ° C and 20 ° C, preferably between 0 and 10 ° C.
• the decomposition temperature of the diazonium salt can vary between room temperature and 150 ° C, preferably between 40 ° C and 130 ° C.
• room temperature is generally meant a temperature between 15 ° C and 25 ° C.
• the duration of the heat treatment advantageously varies between 5 minutes and 4 hours, preferably between 15 minutes and 2 hours.
• the process of the invention is carried out at atmospheric pressure but preferably under a controlled atmosphere of inert gases such as nitrogen or rare gases, for example argon. A pressure slightly higher or lower than atmospheric pressure may be suitable.
• one of them comprises the formation of a diazonium salt from the compound aminoaromatic then thermal decomposition of said salt in the reaction medium.
• the boron trifluoride source, the aminoaromatic compound and the organic solvent are introduced in any order; the nitrosating agent is introduced and the reaction medium is subjected to a heat treatment in order to decompose the diazonium salt obtained without it leaving the medium; the fluoroaromatic compound obtained is recovered.
• the source of boron trifluoride is charged, preferably in the form of a complex and at low temperature for reasons of convenience of handling.
• the temperature is advantageously chosen between -10 ° C and 20 ° C, preferably between 0 and 10 ° C, with the exception of boron trifluoride in the form of dihydrate which is introduced at room temperature.
• the aminoaromatic compound is then added, all at once or gradually. Progressive addition is preferred.
• the aminoaromatic compound can be introduced alone or in solution in all or part of the organic solvent used in an amount representing, for example, from 50 to 100% by weight of the total amount of solvent employed.
• the nitrosating agent is then added, all at once or gradually. Progressive addition is preferred.
• the nitrosating agent can be introduced alone or in solution in the organic solvent used, for example, between 0 and 50% by weight.
• An arenediazonium or heteroarenediazonium salt is obtained which precipitates. It preferably responds to the following formula (III):
• - A, R, m have the meanings given above
• - X can be a salt derived from BF 3 or an alcoholate part (R a -0 " ) originating from alkyl nitrite.
• the reaction medium is subjected to a heat treatment in order to decompose the diazonium salt obtained without it leaving the medium, heating in the temperature zone previously defined, namely between room temperature and 150 ° C., preferably between 40 ° C. and 130 ° C.
• the fluoroaromatic compound (IV) is obtained which corresponds to the formula:
• formula (IV) includes the compounds obtained from aminoaromatic compounds corresponding to formulas (la) and (Ib).
• the fluoroaromatic compound is obtained in organic solution. It is recovered according to conventional separation techniques, preferably by distillation. According to an embodiment which is preferred, the process of the invention is carried out by decomposing the diazonium salt as it is formed in the reaction medium.
• the implementation of the substrate, the source of boron trifluoride, the organic solvent is identical. The source of boron trifluoride is charged, preferably at low temperature, then the aminoaromatic compound is added alone or in organic solution, all at once or gradually. Progressive addition is preferred.
• the mixture is heated to bring the reaction medium to the decomposition temperature of the diazonium salt: the temperature being chosen between room temperature and 150 ° C, preferably between 40 ° C and 130 ° C.
• the nitrosating agent preferably an alkyl nitrite
• the duration of the heat treatment which includes the rise in temperature and the addition of the third reagent advantageously varies between 5 minutes and 4 hours, preferably between 15 minutes and 2 hours.
• the reaction is continued until complete disappearance of gas evolution (nitrogen possibly boron trifluoride). Heating can be continued for this purpose.
• An arenediazonium or heteroarenediazonium salt is obtained intermediately which preferably corresponds to formula (III) which is only present in the reaction medium in a very small amount since it is rapidly decomposed.
• the order of magnitude of the concentration of diazonium salt will be specified approximately ten times lower than the concentration of starting aminoaromatic compound.
• the fluoroaromatic compound is obtained which preferably corresponds to formula (IV), in organic solution. It is conventionally recovered as described above.
• the source of boron trifluoride, the nitrosating agent and the organic solvent are introduced in any order and then the mixture is heated to the decomposition temperature of the salt.
• the process of the invention is particularly interesting because it makes it possible to obtain fluoroaromatic compounds which are difficult to access in particular due to the presence of fragile groups (for example CO) or the fluorinated nitrogen heterocyclic compounds.
• the process of the invention has many advantages. It saves a step of separating the diazonium salt. It better meets safety requirements because the diazonium salt is not isolated and preferably decomposed as it is formed, which reduces the risk of explosion or thermal runaway. It is less polluting than previous processes because it does not use any acid source except BF 3 which, by neutralization, leads to the formation of easily isolable mineral salts.
• the conversion rate (TT) corresponds to the ratio between the number of moles of substrate transformed and the number of moles of substrate used.
• the yield (RR) corresponds to the ratio between the number of moles of product formed and the number of moles of substrate used.
• Example 1 Preparation of m-fluorotoluene. 534 mg (4.98 mmol) of m-toluidine in 2.96 g of o-dichlorobenzene (o) are slowly introduced into a three-necked flask equipped with a condenser, a thermocouple and a stirring system. -DCB) in 5 min on a foot of 1.05 g (7.42 mmol, 1.5 mol eq.) Of BF 3 , and 2 0 at a temperature of -15 ° C.
• C.A. aminoaromatic compound.
• Example 7 The procedure of Example 1 is reproduced according to the conditions defined in Table (II). The results are reported in Table (II).
• CA amino aromatic compound.
• Example 9 Preparation of m-fluorotoluene. 284 mg (2.62 mmol) of m-toluidine in 3.03 g of o-dichlorobenzene are introduced into a 25 mL three-necked flask equipped with a condenser, a thermocouple and a stirring system. one 400.2 mg (3.85 mmol, 1.47 mol eq.) foot of BF 3 , 2H 2 0 at room temperature and drop by drop in 6 minutes. At the end of pouring, the solution is pink with a precipitate. The reaction medium is then heated to 100 ° C., then after 20 minutes, is added at 100 ° C.
• Example 10 Preparation of 2-chloro-5-fluoropyridine.
• a 25 mL three-necked flask equipped with a condenser, a thermocouple and a stirring system 1 g (7.78 mmol) of 2-chloro-5-aminopyridine is introduced into 14.3 g of o-dichlorobenzene at a distance of 1.64 g (11.5 mmol, 1.47 eq. mol.) of BF 3 Et 2 0 at room temperature drop by drop within 5 minutes.
• the solution is beige with a precipitate.
• the reaction medium is then heated to 105 ° C.
• Example 11 Preparation of 3-fluoroquinoline.
• 1 g (6.94 mmol) of 3-aminoquinoline is introduced into a 50 ml three-necked flask equipped with a condenser, a thermocouple and a stirring system.
• the reaction medium is then heated to 50 ° C. and then 1.2 ml (9.01 mmol, 1.3 mol eq.) Of t-butyl nitrite (90% purity) is added at this temperature over 30 minutes. ).
• the reaction medium is brought to 100 ° C. and stirred for 1 hour.
• the yield of isolated product is 40%.
• Example 12 Preparation of 3-fluoro-6-methoxyquinoline. 224 mg (1.29 mmol) of 3-amino-6-methoxyquinoline in 2.5 ml of o- are introduced into a 25 ml three-necked flask equipped with a condenser, a thermocouple and a stirring system. dichlorobenzene on a 125 ⁇ L (1.97 mmol, 1.5 mol eq.) foot of BF 3 , 2H 2 0 at room temperature and drop by drop in 5 minutes. The reaction medium is then heated to 40 ° C.

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