Patent Description:
Trifluoromethylated aromatic compounds belong amongst industrially important compounds used for the production of organic pigments, pesticides and drugs. However, trifluoromethylated aromates are biologically active (toxic) compounds which, when they contaminate water, increase the COD parameter and the content of organically bound fluorine, while being very poorly biodegradable or not biodegradable at all.

Chemical oxidation processes are often used to decompose difficult-to-biodegrade aromatic compounds in wastewater. However, efficient removal of aromatic trifluoromethyl derivatives by chemical oxidation methods requires the application of large excesses of these oxidizing agents, as the C-H and C-C bonds tend to be much more prone to oxidation than carbon-fluorine (generally carbon-halogen) bonds. This results in unbearably high costs for a sufficiently efficient chemical oxidation process, with a large excess of oxidizing agents (usually up to <NUM> times the stoichiometry) required to cleave the C-F bonds of the contaminants, leading to complete mineralization of organic contaminants to inorganic oxidation products (carbon dioxide, water, hydrogen halides or salts thereof, etc.), as described, for example, in: <NPL>.

Reductive techniques, on the other hand, lead to conversion of aromatic fluorinated derivatives into defluorinated organic products, which are usually less toxic (biologically less active) and significantly more biodegradable, allowing a much smaller excess of reducing agents to be used, and subsequent use of the cheapest biological degradation processes by common techniques used in wastewater treatment plants.

Therefore, the use of reductive processes is a very efficient and economically interesting technique for the degradation of aromatic trifluoromethyl derivatives. Its main advantage is its high selectivity (under appropriately selected reaction conditions only carbon-halogen bond cleavage occurs), which allows the use of only a small excess of effective reducing agent for the desired hydrodefluorination.

Currently, processes based on the application of base metals in the form of nanoparticles are also being investigated for hydrodefluorination of polyfluorinated derivatives. Nanoparticles of base metals (e.g. iron) hydrodefluorinate the fluorinated derivatives only very slowly and with low conversion rates, therefore it is necessary to use an enormous excess for efficient hydrodefluorination, as described e.g. in <NPL>.

For reductive hydrodefluorination, processes in anhydrous aprotic solvents are described using hydrides of elements of groups <NUM> and <NUM> (especially organometallic compounds of silicon, tin, aluminum). To carry out this reaction it is often necessary to use expensive catalysts based on platinum metals (e.g. <NPL>), alternatively, nickel coordination compounds are also reported as catalytically active (e.g. <NPL>), or Lewis acids of unusual structure (<NPL>.

<NPL> describes the preparation of p-cresol from trifluoromethylphenol using Raney Ni-Al alloy in an alkaline solution, wherein mostly hydrolysis of CF3-group occurs with only minor occurence of hydrodefluorination.

All of the above hydrodefluorination processes are very far from the possibility of practical use for decontamination processes.

Thus, there remains a need to find a process for hydrodefluorination of aromatic trifluoromethyl derivatives that is economically effective, provides biodegradable products, and is efficient.

Object of the present invention is a method of hydrodefluorination (i.e. reductive cleavage of C-F bond) of aromatic trifluoromethyl compounds of formula I
<CHM>.

The resulting aqueous phase contains less than <NUM> % of the initial amount of the compound of formula I and organic compounds comprising C-F bonds.

The component A is preferably Raney Al-Ni alloy with weight ratio of Al:Ni = <NUM>:<NUM>, i.e. <NUM> wt. % Al and <NUM> wt. % Ni, or nickel bronze, alloys containing the metals CuAlNiFe and optionally Mn, preferably with molar ratio Al:Ni = <NUM>:<NUM> or higher, such as CuAl<NUM>Ni<NUM>Fe<NUM>.

The component A is preferably added in smaller portions, for example in two or three or four or five portions.

In some embodiments, in addition to components A and B, an auxiliary reducing agent (component C) is added to the mixture in step (a), in order to reduce other reducible functional groups than CF<NUM>, which may be contained in the compound of formula I (such as C-halogen bonds wherein halogen is other than F, - NO<NUM>, -N=N-, carbonyl group, alkene (-C=C-)). Use of the auxiliary reducing agent allows to achieve a complete reduction of the compound of formula I at lower ratios of component A to the compound of formula I, because the reducing agent A is not consumed by reducing other than C-F bonds.

When the auxiliary reducing agent (component C) is used, any water-soluble base (component B) selected from alkali metal hydroxides and/or carbonates can be used. When no auxiliary reducing agent is used, use of alkali metal hydroxide as component B results in a higher effectiveness.

Component C, the auxiliary reducing agent, is preferably selected from the group comprising tetrahydroborates (e.g. NaBH<NUM>, KBH<NUM>), secondary C3-C6 alcohols (e.g. isopropyl alcohol, <NUM>-hydroxy-<NUM>,<NUM>-dioxolane), elemental aluminium, technical grade iron (including nanoFe), ferrous(II) sulfate, ferrous(II) chloride, magnesium, Devarda's Al-Cu-Zn alloy (with content of <NUM>-<NUM> wt. % Al, <NUM>-<NUM> wt. % Zn and <NUM>-<NUM> wt. %Cu), Arnd's alloy Cu-Mg (with content of <NUM>-<NUM> wt. % Cu and <NUM>-<NUM> wt. % Mg), hydrazine and salts thereof with formic, sulfuric or hydrochloric acids, phosphinic acid and salts thereof with alkali metals, and/or reducing saccharides (e.g. glucose).

In some embodiments, step (a) is preceded by a pre-treatment step comprising reduction of other reducible functional groups than CF<NUM>, which may be contained in the compound of formula I (such as C-halogen bonds wherein halogen is other than F, -NO<NUM>, -N=N-, carbonyl group, alkene (-C=C-)) by applying the component C together with an undissolved (water-insoluble) part of once used (i.e., recycled) component A. The recycled component A typically contains predominantly Ni.

The pre-treatment step may be carried out instead of adding the component C in the step (a), or in addition to adding the component C to the mixture in the step (a).

Component B (base) is preferably selected from the group comprising sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, and mixtures thereof.

Preferably, the pH value of the separated aqueous phase of the reaction mixture is adjusted to pH in the range of <NUM> to <NUM>, using a acidic-reacting agent selected from the group comprising saturation by gas mixtures comprising CO<NUM> (e.g. flue gas separated from the solids), aqueous solution of sulfuric acid, aqueous solution of hydrochloric acid, aqueous solution of phosphoric acid, or aqueous solution of nitric acid.

The invention thus provides a procedure of AOX dehalogenation using a reducing agent, under catalysis by nickel prepared in situ from the component A, e.g., from Raney Al-Ni alloy.

)Ar-CF<NUM> + n Al-Ni + 3n OH- + n H<NUM>O → (subst. )Ar-CH<NUM> + n Al(OH)<NUM>- + <NUM> F-.

Dissolved aluminium is removed from the aqueous phase together with nickel microparticles by means of neutralization (or slight acidification) to pH = <NUM> to <NUM>, preferably <NUM> to <NUM>, according to the following equation:
<CHM>.

Within the framework of the present invention, it was found that this process leads to a complete reductive defluoration of compounds of formula I, and simultaneously leads to a complete removal of the unreacted agents. The process may easily be scaled up.

Filtration was performed using KA <NUM> filter paper, manufactured by Papirna Pernštejn, s. , or using filter cloth PP010308 produced by ECE Group.

Comparative examples show the use of either Raney nickel with an alternative reducing agent or an attempt to replace the Al-Ni alloy by an alternative hydrodefluorinating agent.

Data shown in % are given in % by weight, unless otherwise stated.

To <NUM> of aqueous solution containing <NUM> mmol/l of <NUM>-chloro-<NUM>-(trifluoromethyl)aniline and <NUM> mol/l of isopropyl alcohol was added <NUM> of Raney Al-Ni alloy and <NUM> of aqueous <NUM> mol/l NaOH solution with vigorous stirring. After stirring for <NUM> minutes, a second portion of <NUM> of Al-Ni alloy was added, and after additional <NUM> minutes of stirring, a third portion <NUM> of Al-Ni alloy was added. After stirring for further <NUM> minutes, further <NUM> of <NUM> mol/l NaOH was added to the suspension, and the suspension was stirred for <NUM> hours.

A portion of the filtrates (<NUM>) was extracted with dichloromethane (3x <NUM> CH<NUM>Cl<NUM>). Subsequently, the dichloromethane extract was concentrated and evaporated to dryness. According to <NUM>H and <NUM>F NMR analysis of the residue, quantitatively dissolved in hexadeuteriosulfoxide, this residue of the dichloromethane extract contains only <NUM>-methylaniline (p-toluidine, i.e. pure product of hydrodefluorination).

The remaining filtrates were neutralized with <NUM>% phosphoric acid to pH = <NUM>, then subjected to ICP-OES analysis, which showed a residual Ni content below <NUM> Ni/l and an Al content below <NUM> Al/l.

To <NUM> of aqueous solution containing <NUM> mmol/l of <NUM>-chloro-<NUM>-(trifluoromethyl)aniline and <NUM> mol/l of isopropyl alcohol, <NUM> of Devarda's Al-Cu(Zn) alloy and <NUM> of <NUM> mol/l aqueous NaOH solution were added with vigorous stirring. After stirring for <NUM> minutes, a second portion of <NUM> of Devarda's Al-Cu(Zn) alloy was added, and after additional <NUM> minutes of stirring, a third portion of <NUM> of Devarda's Al-Cu(Zn) alloy was added. After stirring for further <NUM> minutes, further <NUM> of <NUM> mol/l NaOH was added to the suspension, and the suspension was stirred for <NUM> hours.

A portion of the filtrates (<NUM>) was extracted with dichloromethane (3x <NUM> CH<NUM>Cl<NUM>). Subsequently, the dichloromethane extract was concentrated and evaporated to dryness. According to <NUM>H and <NUM>F NMR analysis of the residue quantitatively dissolved in hexadeuteriosulfoxide, this residue of the dichloromethane extract contains only unreacted <NUM>-chloro-<NUM>-(trifluoromethyl)aniline.

The remaining filtrates were neutralized with <NUM>% phosphoric acid to pH = <NUM>, then subjected to ICP-OES analysis, which showed a residual Cu content below <NUM> Cull, Al content below <NUM> Al/l and Zn content below <NUM> Zn/l.

To <NUM> of aqueous solution containing <NUM> mmol/l of <NUM>,<NUM>-dichloro-<NUM>-(trifluoromethyl)aniline and <NUM> mol/l of isopropyl alcohol, <NUM> of Raney Al-Ni alloy and <NUM> of <NUM> mol/l aqueous NaOH solution were added with vigorous stirring. After stirring for <NUM> minutes, a second portion of <NUM> of Al-Ni alloy was added, followed by a third portion of <NUM> of Al-Ni alloy after an additional <NUM> minutes of stirring, this was repeated a total of <NUM> times. After stirring for further <NUM> minutes, further <NUM> of <NUM> mol/l NaOH were added to the suspension and the suspension was stirred for <NUM> hours.

A portion of the filtrates (<NUM>) was further extracted with dichloromethane (3x <NUM> CH<NUM>Cl<NUM>). Subsequently, the dichloromethane extract was concentrated and evaporated to dryness. According to <NUM>H and <NUM>F NMR analysis of the residue quantitatively dissolved in hexadeuteriosulfoxide, this residue of the dichloromethane extract contains only <NUM>-methylaniline (p-toluidine, i.e. pure product of hydrodefluorination).

The remaining filtrates were neutralized with <NUM>% sulfuric acid to pH = <NUM>, then subjected to ICP-OES analysis, which showed a residual Ni content below <NUM> Ni/l and an Al content below <NUM> Al/l.

To <NUM> of aqueous solution containing <NUM> mmol/l of <NUM>-(trifluoromethyl)aniline, <NUM> of Raney Al-Ni alloy and after stirring <NUM> of <NUM> mol/l aqueous NaOH solution were added during <NUM> seconds with vigorous stirring (i.e., a total of <NUM> mmol NaOH). After stirring for <NUM> hours, a second portion of <NUM> of <NUM> mol/l aqueous NaOH solution was added. After <NUM> hours of stirring, <NUM> of dichloromethane was added, the suspension was stirred and separated by sedimentation. After the separation, the dichloromethane phase was taken for analysis of aromatic compounds content. The sedimented solid phase was extracted <NUM> more times with <NUM> of CH<NUM>Cl<NUM> each time, the liquid phase was always added to the aqueous phase forming the upper layer in a separatory funnel, the liquid phases were shaken vigorously for <NUM> minutes and the lower dichloromethane phase was separated and the dichloromethane extracts were collected. Subsequently, the combined dichloromethane extracts were concentrated and evaporated to dryness. According to <NUM>H and <NUM>F NMR analysis of the residue quantitatively dissolved in deuteriochloroform, this residue of dichloromethane extract contains <NUM>-methylaniline.

The aqueous phase was neutralized with <NUM>% sulfuric acid to pH = <NUM>, then the resulting precipitate was filtered off and the filtrates were subjected to ICP-OES analysis, which showed a residual Ni content below <NUM> Ni/l and an Al content below <NUM> Al/l.

To <NUM> of an aqueous solution containing <NUM> mmol/l of <NUM>-chloro-<NUM>-(trifluoromethyl)phenol and <NUM> mol/l ofNaOH were added, with vigorous stirring, <NUM> of Raney Al-Ni alloy and <NUM> of a commercial aqueous solution of NaBH<NUM> (content <NUM> wt. %) in <NUM> MNaOH. The resulting suspension was further stirred for <NUM> hours and then warmed to <NUM> over <NUM> minutes. After cooling, <NUM> of dichloromethane were added to the suspension, followed by acidification of the reaction mixture with <NUM>% aqueous sulfuric acid solution, and the resulting suspension was stirred and separated by sedimentation. After separating the liquid phase, the dichloromethane layer was separated for analysis of aromatics content. The sedimented solid phase was extracted <NUM> times with <NUM> of CH<NUM>Cl<NUM>, the liquid phases were added to the aqueous phase forming the upper layer in a separatory funnel. The liquid phases were shaken vigorously for <NUM> minutes each time and the separated dichloromethane phases were collected. Subsequently, the combined dichloromethane extracts were concentrated and evaporated to dryness. According to <NUM>H and <NUM>F NMR analysis of the residue quantitatively dissolved in hexadeuteriosulfoxide, this dichloromethane extract residue contains only organic hydrodefluorination products which do not give any signal in the <NUM>F NMR spectrum.

To <NUM> of an aqueous solution containing <NUM> mmol/l <NUM>-chloro-<NUM>-(trifluoromethyl)phenol and <NUM> NaOH was added, under vigorous stirring, <NUM> of a <NUM>% aqueous suspension of Raney nickel (supplied by Riedel-de Haen), <NUM> of aluminum powder and <NUM> of Devarda's Al-Cu-Zn alloy. <NUM> (<NUM>) of a commercial aqueous solution containing <NUM>% by weight of NaBH<NUM> in <NUM> mol/l NaOH was added to the resulting suspension, and the suspension was further stirred for <NUM> hours.

<NUM> of dichloromethane were added to the suspension, followed by acidification of the reaction mixture with <NUM>% aqueous sulfuric acid solution, the resulting suspension was stirred and separated by sedimentation. After removing the liquid phase, the dichloromethane layer was separated for analysis of aromatics content. The sedimented solid phase was extracted <NUM> times with <NUM> of CH<NUM>Cl<NUM>, the liquid phase was added to the aqueous phase forming the upper layer in a separatory funnel, the liquid phases were shaken vigorously for <NUM> minutes and the separated dichloromethane phases were collected.

Subsequently, the combined dichloromethane extracts were concentrated and evaporated to dryness. According to <NUM>H and <NUM>F NMR analysis of the residue quantitatively dissolved in hexadeuteriosulfoxide, this residue of dichloromethane extract contains only unreacted <NUM>-chloro-<NUM>-(trifluoromethyl)phenol and <NUM>-(trifluoromethyl)phenol, in the <NUM>F NMR spectrum there are also <NUM> signals having chemical shifts -<NUM> ppm and -<NUM> ppm.

To <NUM> of an aqueous solution containing <NUM> mmol/l of <NUM>-nitro-<NUM>-(trifluoromethyl)phenol and <NUM> mol/l of NaOH was added, with vigorous stirring, <NUM> of <NUM> aqueous NaOH solution and then dropwise <NUM> of an aqueous solution of FeSO<NUM> at a concentration of <NUM> mol/l. The resulting green suspension was stirred in the reaction vessel for <NUM> hours, then <NUM> of Raney Al-Ni alloy was added and the resulting suspension was further stirred for <NUM> hour and then heated to <NUM> over <NUM> minutes. After the reaction mixture was cooled, <NUM> of dichloromethane was added to the suspension, followed by acidification of the reaction mixture with <NUM>% aqueous sulfuric acid solution, and the resulting suspension was stirred and separated by sedimentation. After removing the liquid phase, the dichloromethane layer was separated for analysis of aromatics content. The sedimented solid phase was extracted <NUM> times with <NUM> of CH<NUM>Cl<NUM>, the liquid phase was added to the aqueous phase forming the upper layer in a separatory funnel, the liquid phases were shaken vigorously for <NUM> minutes and the separated dichloromethane phases were collected. Subsequently, the combined dichloromethane extracts were concentrated and evaporated to dryness. According to <NUM>H and <NUM>F NMR analysis of the residue quantitatively dissolved in hexadeuteriosulfoxide, this dichloromethane extract residue contains only organic products which do not give any signal in the <NUM>F NMR spectrum.

To <NUM> of an aqueous solution containing <NUM> mmol/l of <NUM>-nitro-<NUM>-(trifluoromethyl)phenol and <NUM> mol/l of NaOH was added, with vigorous stirring, <NUM> of <NUM> aqueous NaOH solution and then dropwise <NUM> of an aqueous solution of FeSO<NUM> at a concentration of <NUM> mol/l, and the resulting green suspension was stirred in the reaction vessel for <NUM> hours. Then <NUM> of Raney Al-Ni alloy was added and the resulting suspension was further stirred for <NUM> hour and then tempered to <NUM> over <NUM> minutes. After the reaction mixture was cooled, <NUM> of dichloromethane was added to the suspension, followed by acidification of the reaction mixture with <NUM>% aqueous sulfuric acid solution, and the resulting suspension was stirred and separated by sedimentation. After removing the liquid phase, the dichloromethane layer was separated for analysis of aromatics content. The sedimented solid phase was extracted <NUM> times with <NUM> of CH<NUM>Cl<NUM>, the liquid phase was added to the aqueous phase forming the upper layer in a separatory funnel, the liquid phases were shaken vigorously for <NUM> minutes and the separated dichloromethane phases were collected. Subsequently, the combined dichloromethane extracts were concentrated and evaporated to dryness. According to <NUM>H and <NUM>F NMR analysis of the residue quantitatively dissolved in hexadeuteriosulfoxide, this dichloromethane extract residue contains only organic products which do not yield any signal in the <NUM>F NMR spectrum.

To <NUM> of an aqueous solution containing <NUM> mmol/l of <NUM>-nitro-<NUM>-(trifluoromethyl)phenol and <NUM> mol/l of NaOH was added, with vigorous stirring, <NUM> of <NUM> aqueous NaOH solution and <NUM> of glucose monohydrate, the solution was heated to <NUM> for <NUM> hours. The solution was then cooled to <NUM>, and <NUM> of Raney Al-Ni alloy was added thereto, and the resulting suspension was further stirred for <NUM> hour and then heated to <NUM> over <NUM> minutes. After cooling the reaction mixture, <NUM> of dichloromethane was added to the suspension, followed by acidification of the reaction mixture with <NUM>% aqueous sulfuric acid solution, and the resulting suspension was stirred and separated by sedimentation. After removing the liquid phase, the dichloromethane layer was separated for analysis of aromatics content. The sedimented solid phase was extracted <NUM> times with <NUM> of CH<NUM>Cl<NUM>, the liquid phase was added to the aqueous phase forming the upper layer in a separatory funnel, the liquid phases were shaken vigorously for <NUM> minutes and the separated dichloromethane phases were collected. Subsequently, the combined dichloromethane extracts were concentrated and evaporated to dryness. According to <NUM>H and <NUM>F NMR analysis of the residue quantitatively dissolved in hexadeuteriosulfoxide, this dichloromethane extract residue contains only organic products which do not yield any signal in the <NUM>F NMR spectrum.

To <NUM> of an aqueous solution containing <NUM> mmol/l of <NUM>-fluoro-<NUM>-(trifluoromethyl)benzylamine and <NUM> mol/l of isopropyl alcohol, <NUM> of Raney Al-Ni alloy and <NUM> of aqueous <NUM> mol/l NaOH solution were added with vigorous stirring. After stirring for <NUM> minutes, a second portion of <NUM> of Al-Ni alloy was added, and after an additional <NUM> minutes of stirring, a third portion <NUM> of Al-Ni alloy was added. After stirring for further <NUM> minutes, further <NUM> of <NUM> mol/l NaOH were added to the suspension and the suspension was further stirred for <NUM> hours.

Subsequently, after cooling, the filtrates obtained were extracted with dichloromethane (3x <NUM> CH<NUM>Cl<NUM>). Subsequently, the dichloromethane extract was concentrated and evaporated to dryness. According to <NUM>H and <NUM>F NMR analysis of the residue quantitatively dissolved in hexadeuteriosulfoxide, this residue of the dichloromethane extract contains <NUM>-methyl-benzylamine, i.e. the hydrodefluorination product.

The remaining aqueous phase after extraction with dichloromethane was neutralized with <NUM>% sulfuric acid (obtained by mixing <NUM> volume of concentrated sulfuric acid with <NUM> parts of water) to pH = <NUM>, the filtrates obtained by separating the formed precipitate were subsequently subjected to ICP-OES analysis showing the residual content of Ni below <NUM> Ni/l and the Al content below <NUM> Al/l.

To <NUM> of an aqueous solution containing a mixture of <NUM> mmol/l <NUM>-CF<NUM>-benzoic acid and <NUM> mmol/l <NUM>-CF<NUM>-benzoic acid in <NUM> mmol/l KOH was added <NUM> of Raney Al-Ni alloy and <NUM> of aqueous <NUM> mol/l KOH solution. After stirring for <NUM> minutes, a second portion of <NUM> of Al-Ni alloy was added to the reaction mixture, followed by an additional <NUM> of a <NUM> mol/l aqueous NaOH solution, and the suspension was further stirred for <NUM> hours.

Subsequently, after cooling, the filtrates obtained were acidified with <NUM>% sulfuric acid to pH = <NUM>-<NUM>, extracted with dichloromethane (3x <NUM> CH<NUM>Cl<NUM>). Subsequently, the dichloromethane extract was concentrated and evaporated to dryness. According to <NUM>H and <NUM>F NMR analysis of the residue quantitatively dissolved in hexadeuteriosulfoxide, this residue of the dichloromethane extract contains <NUM>-methylbenzoic acid and <NUM>-methylbenzoic acid, i.e. hydrodefluorination products.

To <NUM> of a <NUM>:<NUM> water: isopropyl alcohol solution containing <NUM> mmol/l of <NUM>-chloro-<NUM>-(trifluoromethyl)aniline, <NUM> of a commercial aqueous solution of NaBH<NUM> containing <NUM>% by weight of NaBH<NUM> in <NUM> mol/l NaOH were added with vigorous stirring. The mixture was stirred and then <NUM> of Raney Al-Ni alloy was added. After stirring for further <NUM> hours, <NUM> of dichloromethane were added to the reaction mixture, the suspension was stirred and separated by sedimentation. After removing the liquid phase, the dichloromethane layer was separated for analysis of aromatics content. The sedimented solid phase was extracted <NUM> times with <NUM> of CH<NUM>Cl<NUM>, the liquid phase was added to the aqueous phase forming the upper layer in a separatory funnel, the liquid phases were shaken vigorously for <NUM> minutes and the separated dichloromethane phases were collected. Subsequently, the dichloromethane extract was concentrated and evaporated to dryness. According to <NUM>H and <NUM>F NMR analysis of the residue quantitatively dissolved in deuteriochloroform, this residue of the dichloromethane extract contains <NUM>-methylaniline.

The aqueous phase was neutralized with <NUM>% sulfuric acid to pH = <NUM>, then the resulting precipitate was filtered off and the filtrates were subjected to ICP-OES analysis, which showed the residual Ni content below <NUM> Ni/l and the Al content below <NUM> Al/l.

To <NUM> of an aqueous solution containing <NUM> mmol/l of <NUM>-(trifluoromethyl)aniline, <NUM> of Raney Al-Ni alloy was added with vigorous stirring. After thorough stirring, <NUM> of K<NUM>CO<NUM> was added in one portion and the mixture was heated to <NUM>, then the heating was stopped. After stirring for further <NUM> hours, <NUM> of dichloromethane were added to the reaction mixture, the suspension was stirred and separated by sedimentation. After removing the liquid phase, the dichloromethane layer was separated for analysis of aromatics content. The sedimented solid phase was extracted <NUM> times with <NUM> of CH<NUM>Cl<NUM>, the liquid phase was added to the aqueous phase forming the upper layer in a separatory funnel, the liquid phases were shaken vigorously for <NUM> minutes and the separated dichloromethane phases were collected. Subsequently, the dichloromethane extract was concentrated and evaporated to dryness. According to <NUM>H and <NUM>F NMR analysis of the residue quantitatively dissolved in deuteriochloroform, this residue of the dichloromethane extract contains <NUM>-methylaniline.

To the insoluble part of reaction mixture from Example <NUM>, <NUM> of an aqueous solution containing <NUM> mmol/l of <NUM>-hydroxy-<NUM>-(trifluoromethyl)benzonitrile and <NUM> mol/l of NaOH was added with vigorous stirring. Subsequently, <NUM> mmol of hydrazine hydrate and <NUM> mmol of formic acid was added under vigorous stirring. The reaction mixture was stirred in the reaction vessel for <NUM> hours over <NUM> °C under reflux, then cooled below <NUM> and <NUM> of aqueous <NUM> mol/l NaOH and <NUM> of Raney Al-Ni alloy were added under vigorous stirring. The resulting suspension was further stirred for <NUM> hours and then heated to <NUM> over <NUM> minutes. After the reaction mixture was cooled, <NUM> portion of reaction mixture was collected. Subsequently, <NUM> of dichloromethane was added to the collected sample, followed by acidification of the reaction mixture with <NUM>% aqueous sulfuric acid solution, and the resulting suspension was stirred and separated by sedimentation. After removing the liquid phase, the dichloromethane layer was separated for analysis of aromatics content. The sedimented solid phase was extracted <NUM> times with <NUM> of CH<NUM>Cl<NUM>, the liquid phase was added to the aqueous phase forming the upper layer in a separatory funnel, the liquid phases were shaken vigorously for <NUM> minutes and the separated dichloromethane phases were collected. Subsequently, the combined dichloromethane extracts were concentrated and evaporated to dryness. According to <NUM>H and <NUM>F NMR analysis of the residue quantitatively dissolved in hexadeuteriosulfoxide, this dichloromethane extract residue contains only organic product <NUM>-hydroxy-<NUM>-methyl-benzylamine which do not give any signal in the <NUM>F NMR spectrum.

To the insoluble part of reaction mixture from Example <NUM>, <NUM> of solution containing <NUM> mmol/l of <NUM>'-(trifluoromethyl)acetophenone dissolved in <NUM> vol. % aqueous methanol and subsequently <NUM> mmol of powdered NaBH<NUM> was added under vigorous stirring and stirred under heating at <NUM>-<NUM> for <NUM> hours. Subsequently, after cooling to <NUM> °C, <NUM> of Raney Al-Ni alloy and <NUM> of aqueous <NUM> mol/l KOH solution were added. After stirring for <NUM> minutes, a second portion of <NUM> of Raney Al-Ni alloy was added to the reaction mixture, followed by an additional <NUM> of a <NUM> mol/l aqueous NaOH solution, and the suspension was further stirred for <NUM> hours.

Claim 1:
A method of hydrodefluorination of aromatic trifluoromethyl compounds of formula I
<CHM>
wherein A, B, X, G and Z are independently selected from the group comprising H, I, Br, F, Cl, CF<NUM>, COOR, NO<NUM>, N=N-R, SO<NUM>R, CH<NUM>R, OR, NR<NUM>, CH<NUM>NR<NUM>, R-C=O, CN;
wherein R is H, C<NUM>-C<NUM> alkyl, C<NUM>-C<NUM> aryl, or C<NUM>-C<NUM> heterocyclyl containing one to four heteroatoms independently selected from O, S, N;
in alkaline aqueous environment, said method comprising the steps of:
a) adding to an aqueous or colloid solution of the compound of formula I, at temperature within the range of <NUM> to <NUM> a mixture comprising:
- component A, which is an alloy containing aluminium (Al) acting as reducing agent and nickel (Ni) acting as hydrodefluoration catalyst, wherein the molar ratio of CF<NUM> : Al is within the range of <NUM> mol of CF<NUM> to <NUM> or more mol Al, and the molar ratio of CF<NUM> : Ni is within the range of <NUM> mol CF<NUM> to <NUM> or more mol Ni;
- component B, which is at least one alkali metal hydroxide or carbonate in molar ratio to Al <NUM>:<NUM> to <NUM>:<NUM>, wherein the amount used corresponds to pH of the reaction mixture higher than <NUM>;
b) stirring the resulting reaction mixture at a temperature within the range of <NUM> to <NUM>, for at least <NUM> minutes and at most <NUM> hours;
c) separating the nickel sludge from the aqueous phase of the reaction mixture;
d) adjusting pH of the separated aqueous phase of the reaction mixture to a value within the range of <NUM> to <NUM>, which causes precipitation of insoluble aluminium salts which adsorb microparticles of nickel and organic compounds from the mixture, and separating the precipitate.