Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
  • C07C49/20—Unsaturated compounds containing keto groups bound to acyclic carbon atoms
  • C07C49/227—Unsaturated compounds containing keto groups bound to acyclic carbon atoms containing halogen
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
  • C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
  • C07C45/32—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen
  • C07C45/37—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of >C—O—functional groups to >C=O groups
  • C07C45/39—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of >C—O—functional groups to >C=O groups being a secondary hydroxyl group

Definitions

• the present invention relates to a process for the preparation of ⁇ -halogenated ketones from ⁇ -halogenated secondary alcohols.
• the invention relates more particularly to the preparation of ⁇ -trihalogenated ketones from ⁇ -trihalogenated secondary alcohols
• This process suffers from several drawbacks. It comprises several stages, preparation of the organometallic compound from bromobenzene then reaction with trifluoroacetic acid at low temperature (-78 ° C) and hydrolysis which complicates its implementation and it is difficult to transpose to industrial scale.
• the objective of the present invention is to provide a new method which overcomes the aforementioned drawbacks.
• a preferred variant of the process of the invention consists in also adding, as activators, metals such as cadmium, cerium, bismuth, lead, silver, tellurium, tin or germanium.
• An object of the invention is therefore to provide a very general process for obtaining ⁇ -halogenated ketones from ⁇ -halogenated secondary alcohols corresponding to the general formula (I): Y,
• Q represents a monovalent hydrocarbon group, optionally substituted having from 1 to 40 carbon atoms
• the invention also contemplates that the group CY-
• the group -CHOH-CY ⁇ Y 2 Y 3 is called
• the characteristic of the process of the invention consists in carrying out the oxidation of the ⁇ -halogenated secondary alcohols to corresponding ketones in an aqueous or organic medium, in the presence of a catalyst based on a metal M- j chosen from the metals of group 1b and 8 and possibly an activator.
• the ⁇ -halogenated secondary alcohols serving as starting products for the preparation of ketones correspond to the general formula (I) in which Q represents a monovalent hydrocarbon group, substituted or not, which can be an acyclic saturated or unsaturated aliphatic group, linear or branched; a saturated, unsaturated or aromatic, monocyclic or polycyclic carbocyclic or heterocyclic group.
• Q represents a monovalent hydrocarbon group, substituted or not, which can be an acyclic saturated or unsaturated aliphatic group, linear or branched; a saturated, unsaturated or aromatic, monocyclic or polycyclic carbocyclic or heterocyclic group.
• Q preferably represents an aryl group corresponding to the general formula (II):
• - n is an integer from 0 to 5, preferably from 0 to 3,
• R- R represents R-
• a linear or branched alkoxy or thioether group having from 1 to 6 carbon atoms, preferably from 1 to 4 carbon atoms such as methoxy, ethoxy, propoxy, isopropoxy, butoxy, groups. a group of formula - OH
• the groups R? identical or different represent a hydrogen atom, a linear or branched alkyl group having from 1 to 6 carbon atoms and even more preferably from 1 to 4 carbon atoms or a phenyl group and X symbolizes a halogen atom, in particular a chlorine or bromine atom,
• R 3 represents R 3 one of the following more complex groups: in which :
• R represents a valential bond or a divalent, linear or branched, saturated or unsaturated hydrocarbon group having from 1 to 4 carbon atoms such as, for example, methylene ethylene, propylene, isopropylene, isopropylidene, and m is an integer from 0 to 3,.
• R 4 - A - R5 in which: R4 has the meaning given above,
• R 5 represents a linear or branched alkyl group having from 1 to 6 carbon atoms, preferably from 1 to 4 carbon atoms or a group
• and R 2 have the meaning given above.
• the groups R can be identical or different and 2 successive carbon atoms of the benzene ring can be linked together by a cetal bridge such as the methylene dioxy or ethylene dioxy groups extranuclear.
• n is equal to 0, 1 2 or 3.
• - n is equal to 0, 1, 2 or 3,
• - R represents one of the following function groups:
• a linear or branched alkyl group having from 1 to 4 carbon atoms having from 1 to 4 carbon atoms
• a linear or branched alkoxy or thioether group having from 1 to 4 carbon atoms .
• ⁇ -halogenated secondary alcohols corresponding to the general formula (I) in which Q represents an aryl group of general formula (II)
• 2-hydroxy-1-phenyl-trichloromethylcarbinol 2-hydroxy-1- phenyl-trifluromethylcarbinol, 3-hydroxy-1-phenyl-trichloromethylcarbinol, 3-hydroxy-1-phenyl-trifluromethylcarbinol, 4-hydroxy-1-phenyl-trichloromethylcarbinol, 4-hydroxy-1- phenyl-trifluoromethylcarbinol, 2-hydroxy-3-methyl-1-phenyl-trichloromethylcarbinol, 2-hydroxy-3-methyl-1 - phenyl-trifluoromethylcarbinol, 2-hydroxy-4-methyl-1-phenyl- trichloromethylcarbinol, 2-hydroxy-4-methyl-1-phenyl-trifluoromethylcarbinol, 2-hydroxy-4-methyl-1-phenyl-trifluoromethylcarbinol, 2-
• Q can represent a carbocyclic group saturated or comprising 1 or 2 unsaturations in the ring, generally having 3 to 7 carbon atoms, preferably 6 carbon atoms in the cycle; said ring being able to be substituted by 1 to 5 groups R-
• groups Q mention may be made of cyclohexyl or cyclohexene-yl groups, optionally substituted by linear or branched alkyl groups, having from 1 to 4 carbon atoms.
• ⁇ -halogenated secondary alcohols of formula (I) in which Q is a cycloaliphatic group mention may be made in particular of 1- (trichloromethylcarbinol) -l -cyclohexene, 1 - (trifluoromethylcarbinol) -l - cyclohexene , 1- (trichloromethylcarbinol) -1-cyclohexane, 1- (trifluoromethylcarbinol) -l-cyclohexane, 1-methyl-2- (trichloromethylcarbinol) -1- cyclohexene, 1-methyl-2- (trifluormethylcarbinol) -1 - cyclohexene, 1-methyl-2- (trichloromethylcarbinol) -cyclohexane, 1 -methyl-2- (trifluoromethylcarbinol) - cyclohexane, 1-methyl-4-isopropyl-2- (trichloromethylmethylcarbin
• Q can represent an acyclic aliphatic group, saturated or unsaturated, linear or branched. More precisely, Q represents an alkyl, alkenyl, alkadienyl, alkynyl, linear or branched group preferably having from 1 to 12 carbon atoms.
• the hydrocarbon chain can optionally be: - interrupted by one of the following groups: O CO COO -N-, -CO-N
• R 2 has the meaning given above.
• acyclic, saturated or unsaturated, linear or branched aliphatic group may optionally carry a cyclic substituent.
• cycle is meant a carbocyclic or heterocyclic, saturated, unsaturated or aromatic cycle.
• the acyclic aliphatic group can be linked to the cycle by a valential link or by one of the following groups:
• IIR 2 R 2 in these formulas R has the meaning given above.
• cyclic substituents it is possible to envisage cycloaliphatic, aromatic or heterocyclic, in particular cycloaliphatic substituents comprising 6 carbon atoms in the ring or benzene, these cyclic substituents themselves being optionally carriers of 1, 2, 3, 4 or 5 R ⁇ , identical or different, R-
• ⁇ -halogenated secondary alcohols of formula (I) in which Q represents an aliphatic group there may be mentioned in particular: 1,1,1-trifluoro-2-pentanol, 4-methyl-1, 1,1-trichloro-2-pentanol, 1,1,1-tririforo-2-hexanol, 3,3-dimethyl-1,1,1-trifluoro-2-butanol, 2-hydroxy-4-methoxy -1,1,1- trichloro-5-pentanol, 1,1,1-trichloro-2-heptanol, 5-hydroxy 4-methyl-6,6,6- trichloro-3-hexanone, 2-hydroxy -1,1,1-trichloro-4-octanone, 2-hydroxy-6-methyl-1,1,1-trichloro-4-heptanone, 4-ethyl-1,1,1-trichloro-2-hexanol , 3-ethyl-1,1,1-trichloro-2-heptan
• Q can also represent a monovalent heterocyclic group, saturated or not, comprising in particular 5 or 6 atoms in the ring including 1 or 2 heteroatoms such as the nitrogen, sulfur and oxygen atoms, the carbon atoms of the heterocycle which may optionally be substituted, in their entirety or for a part of them only by R- groups
• Q can also represent a polycyclic heterocyclic group defined as being either a group consisting of at least 2 aromatic or non-aromatic heterocycles containing at least one heteroatom in each cycle and forming between them systems ortho or ortho and pericondenses or is a group constituted by at least an aromatic or non-aromatic hydrocarbon cycle and at least one aromatic or non-aromatic heterocycle forming between them ortho or ortho and pericondenses systems.
• ⁇ -halogenated secondary alcohols of formula (I) in which Q represents a heterocyclic group mention may be made of 2-furyl-trichloromethylcarbinol, 2-furyl-trifluoromethylcarbinol, 1 - (5-methylfuryl) - trichloromethylcarbinol, 1- (5-N, N-diethylfuramide) -trichloromethylcarbinol, la (2,2,2-trifluoro-1-ethanol) -3-pyridine, 2-amino-4-hydroxy-6-methyl-5 -
• the starting ⁇ -halogenated secondary alcohols which can be oxidized to ketones according to the method of the invention are obtained by methods described in the literature. In particular, they can be prepared by one or other of the methods of preparation cited by J.H.T. LEDRUT and G. COMBES in "Belgian chemical industry” n ° 6 (1962) p. 635 to 652.
• An acid catalyst such as aluminum chloride can be used to react aromatic hydrocarbons such as veratrole (or 1,2-dimethoxybenzene) with chloral.
• aromatic hydrocarbons such as veratrole (or 1,2-dimethoxybenzene)
• chloral for this type of preparation, we can refer, in addition to the previously cited article, to the article by R. QUELET in the
• the catalysts involved in the process of the invention are based on a metal from group 1b and 8 of the periodic table.
• catalysts based on a metal from group 8 of the periodic table include nickel, noble metals such as ruthenium, rhodium, palladium, osmium, iridium, platinum and their mixtures.
• noble metals such as ruthenium, rhodium, palladium, osmium, iridium, platinum and their mixtures.
• group 1b metals copper is preferred.
• platinum and / or palladium catalysts taken in all the available forms such as for example: platinum black, palladium black, platinum oxide, palladium oxide or the metal noble itself deposited on various supports such as carbon black, calcium carbonate, activated aluminas and silicas or equivalent materials. Carbon black based catalytic masses are particularly suitable.
• the amount of this catalyst to be used expressed by weight of metal M ⁇ relative to that of the compound of formula (I) can vary from 0.01 to 10% and, preferably, from 0.04 to 2%.
• the activator can be chosen from all those mentioned in the aforementioned patents.
• use is made of bismuth, lead and cadmium, in the form of free metals or cations.
• the associated anion is not critical and any derivatives of these metals can be used.
• metal bismuth or its derivatives are used.
• the remainder associated with bismuth n ' is not critical from the moment that it satisfies this condition.
• the activator can be soluble or insoluble in the reaction medium.
• Illustrative compounds of activators which can be used in the process according to the present invention are: bismuth oxides; bismuth hydroxides; the salts of mineral hydracids such as: chloride, bromide, iodide, sulfide, selenide, bismuth tellurium; the mineral oxyacid salts such as: sulfite, sulfate, nitrite, nitrate, phosphite, phosphate, pyrophosphate, carbonate, perchlorate, antimoniate, arsenate, selenite, bismuth selenate; oxyacid salts derived from transition metals such as: vanadate, niobate, tantalate, chromate, molybdate, tungstate, bismuth permanganate.
• the salts of mineral hydracids such as: chloride, bromide, iodide, sulfide, selenide, bismuth tellurium
• Suitable compounds are also salts of aliphatic or aromatic organic acids such as: acetate, propionate, benzoate, salicylate, oxalate, tartrate, lactate, bismuth citrate; phenates such as: bismuth gallate and pyrogallate. These salts and phenates can also be bismuthyl salts.
• binary combinations of bismuth with elements such as phosphorus and arsenic can be used; bismuth-containing heteropolyacids and their salts; aliphatic and aromatic bismuthines are also suitable.
• bismuth vanadate BiVO 4 bismuth BiNbO niobate: bismuth tantalate BiTaO 4 ; bismuth neutral chromate Bi 2 (CrO 4 ); bismuthyl dichromate [(BiO) 2 ] Cr 2 O 7 ; bismuthyl acid chromate H (BiO) CrO 4 ; bismuthyl potassium potassium chromate K (BiO) CrO 4 ; bismuth Bi molybdate (MoO 4 ) 3; bismuth tungstate Bi 2 (WO) 3 ; bismuth sodium sodium molybdate NaBi (MoO 4 ) 2 ; bismuth basic permanganate Bi 2 O 2 (OH) MnO 4 .
• bismuth acetate Bi C 2 H 3 O 2 ) 3; bismuthyl propionate (BiO) C 3 H 5 O 2 ; basic bismuth benzoate C6H 5 CO 2 Bi (OH); bismuthyl salicylate C 6 H 4 CO 2 (BiO) (OH); bismuth oxalate (C 2 O 4 ) 3 Bi 2 ; bismuth tartrate Bi 2 (C 4 H 4 O 6 ) 3 , 6H 2 O; bismuth lactate (C 6 H 9 O 5 ) OBi, 7H 2 O; bismuth citrate C 6 H 5 O 7 Bi.
• bismuth phosphide BiP bismuth arsenide Bi3As; sodium bismuthate NaBiO 3 ; bismuth-thiocyanic acids H [Bi (BNS) 5 ], H 3 [Bi (CNS) e] and their sodium and potassium salts; trimethylbismuthine Bi (CH 3 ) 3 , triphenylbismuthine Bi (C 6 H 5 ) 3 .
• the bismuth derivatives which are preferably used to carry out the process according to the invention are: bismuth oxides; bismuth hydroxides; bismuth or bismuthyl salts of mineral hydracids; bismuth or bismuthyl salts of mineral oxyacids; bismuth or bismuthyl salts of aliphatic or aromatic organic acids; and bismuth or bismuthyl phenates.
• a group of activators which are particularly suitable for carrying out the invention consists of: bismuth oxides Bi 2 ⁇ 3 and Bi 2 O 4 ; bismuth hydroxide Bi (OH) 3 ; neutral bismuth sulfate Bi 2 (SO 4 ) 3 ; bismuth chloride BiCl3; bismuth bromide BiBr3; bismuth iodide Bil 3 ; neutral bismuth nitrate Bi (NO 3) 3, 5H O; bismuthyl nitrate BiO (NO 3 ); bismuthyl carbonate (BiO) 2 CO 3 , O, 5H 2 O; bismuth acetate Bi (C 2 H 3 O 2 ) 3 ; bismuthyl salicylate C 6 H 4 CO 2 (BiO) (OH).
• the quantity of activator used expressed by the quantity of metal contained in the activator relative to the weight of the metal Mi engaged, can vary within wide limits. For example, this amount can be as small as 0.1% and can reach 100% by weight of metal M-
• the method of the invention can be carried out according to several embodiments.
• the starting ⁇ -halogenated secondary alcohol corresponds to formula (I) in which Q is an aryl group and carries at least one hydroxyl group, it is advantageous to react this compound of phenolic type, in salified form.
• the catalytic entity may or may not be formed in situ by successive or simultaneous introduction of the catalyst based on the metal M- j and of the activator.
• the starting ⁇ -halogenated secondary alcohol is not a phenolic compound, it is possible to carry out the oxidation reaction, in an organic solvent, without the introduction of a base. In this case, it is desirable to prepare the catalytic entity consisting of the metal M- beforehand . and activator.
• the oxidation reaction is carried out in an aqueous medium containing in solution a basic agent, and more particularly ammonium hydroxide, alkaline or alkaline-earth bases, among which mention may be made of hydroxides such as sodium, potassium or lithium hydroxide; alkali alkanolates such as sodium or potassium methylate, ethylate, isopropylate and tert-butoxide, sodium or potassium carbonates or bicarbonates and, in general, the salts of alkaline or alkaline-earth bases and weak acids.
• a basic agent and more particularly ammonium hydroxide, alkaline or alkaline-earth bases, among which mention may be made of hydroxides such as sodium, potassium or lithium hydroxide; alkali alkanolates such as sodium or potassium methylate, ethylate, isopropylate and tert-butoxide, sodium or potassium carbonates or bicarbonates and, in general, the salts of alkaline or alkaline-earth bases and weak
• the starting alcohol of formula (I) carries a hydroxyl group which is preferably salified before the implementation of the oxidation reaction.
• sodium or potassium hydroxide is used.
• the proportion of mineral base to be used is preferably such that the ratio between the number of moles OH "and the number of moles of compound of formula (I) varies between 1 and 2.
• the concentration by weight of the alcohol of formula (I) in the liquid phase is usually between 1% and 40%, preferably between 2% and 30%. Practically one way of carrying out the process consists in bringing into contact with molecular oxygen or a gas containing it, for example air, the solution containing the alcohol of formula (I), the basic agent, the catalyst based of metal M ⁇ optionally the activator, according to the proportions indicated above.
• a preferred embodiment of the invention consists first of carrying out the salification of the alcohol of formula (I) before the oxidation reaction. From a practical point of view, the alcohol of formula (I) and the basic agent are charged and the compound is obtained in salified form at room temperature (most often between 15 ° C and 25 ° C).
• the reaction mixture kept under scanning of oxygen or of a gas containing it is brought to the desired reaction temperature.
• the oxidation temperature is preferably chosen, in a temperature range from 40 ° C to 100 ° C.
• the mixture is then stirred at the desired temperature until consumption of an amount of oxygen corresponding to that necessary to transform the carbinol group into a carbonyl group.
• the catalytic mass is separated from the reaction medium, for example by filtration.
• the resulting medium is acidified by adding a protonic acid of mineral origin, preferably hydrochloric acid or sulfuric acid or an organic acid such as, for example, trifluromethanesulfonic acid or l methanesulfonic acid until a pH less than or equal to 5.
• the concentration of the acid is indifferent and use is preferably made of commercial forms.
• ketone compound of formula (III) is then recovered according to conventional techniques, for example by extraction with the aid of an appropriate organic solvent, for example an aromatic hydrocarbon, halogenated or not, and there may be mentioned more particularly toluene or mono- or dichlorobenzene.
• an appropriate organic solvent for example an aromatic hydrocarbon, halogenated or not, and there may be mentioned more particularly toluene or mono- or dichlorobenzene.
• one starts with an ⁇ -halogenated secondary alcohol which is a compound of any aliphatic or aromatic type but which is not of the phenolic type (namely an aromatic compound carrying a hydroxyl group).
• the reaction is advantageously carried out in water or in an organic solvent when the ⁇ -halogenated secondary alcohol is not sufficiently soluble in water, for example a solubility in water, at ambient temperature, less than 20% by weight.
• An organic solvent is used, inert under the reaction conditions and making it possible to at least partially solubilize the starting compound.
• ester type solvents and more particularly butyl acetate, amyl acetate, ethyl phthalate.
• concentration of the starting substrate in the solvent is preferably between 10 and 30% by weight.
• catalytic entity for example by taking a catalyst of a metal Mi deposited on a support, preferably activated carbon, silica or l alumina, then introduce the compound providing the activating element, in the presence of a base, preferably sodium carbonate.
• the catalyst based on a metal M ⁇ and an activator is obtained.
• the catalytic entity can also be reduced by a reducing agent such as, for example, hydrogen, formalin or hydrazine.
• the temperature of the oxidation reaction is preferably chosen in a temperature range from 100 ° C to 160 ° C.
• the compound of formula (I) is charged, the organic solvent and the catalyst.
• the reaction mixture kept under scanning of oxygen or of a gas containing it is brought to the desired reaction temperature.
• the mixture is then stirred at the desired temperature until consumption of an amount of oxygen corresponding to that necessary to transform the carbinol group into a carbonyl group.
• the water formed during the reaction is removed continuously, by distillation or physical entrainment by the gas.
• the invention also relates to the ⁇ -halogenated ketones corresponding to the general formula:
• Q has the meaning given above and Q preferably represents an aliphatic radical as defined above and Y 1 ⁇ Y 2 and Y 3 represent a hydrogen atom or a fluorine atom and Y 1 ⁇ Y 2 and Y 3 represent at least one fluorine atom, preferably three fluorine atoms.
• the conversion rate (TT) corresponds to the ratio between the number of substrates transformed and the number of moles of substrate engaged.
• the yield (RR) corresponds to the ratio between the number of moles of product formed and the number of moles of substrate used.
• the weight of the noble metal is expressed in% by weight relative to the total weight of the catalyst (active phase + support).
• the mixture is heated to 125 ° C. and a current of air is passed through the sky above the reactor. After 6 hours of reaction, the yield (RR) is 99% assayed by gas chromatography.
• Example 1 is repeated, but with a catalyst comprising 5.3% Pd + 3% Bi.
• Example 4 Example 3 is repeated, but using 40 ml of butyl acetate.
• the mixture is heated to 80 ° C. and a stream of air is passed by bubbling through the reaction medium. After 8 hours of reaction, the yield (RR) is 96%.
• the mixture is heated to 125 ° C. and a stream of air is passed through the reaction medium.

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