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WO2002096849A1 - Procede pour produire des aldehydes et des cetones aromatiques par oxydation catalytique de composes aromatiques alkyles - Google Patents

Procede pour produire des aldehydes et des cetones aromatiques par oxydation catalytique de composes aromatiques alkyles Download PDF

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Publication number
WO2002096849A1
WO2002096849A1 PCT/EP2002/004795 EP0204795W WO02096849A1 WO 2002096849 A1 WO2002096849 A1 WO 2002096849A1 EP 0204795 W EP0204795 W EP 0204795W WO 02096849 A1 WO02096849 A1 WO 02096849A1
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WIPO (PCT)
Prior art keywords
alkyl
group
trifluoromethylbenzaldehyde
fluorobenzaldehyde
acid
Prior art date
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Ceased
Application number
PCT/EP2002/004795
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German (de)
English (en)
Inventor
Walther Jary
Eduard Perndorfer
Markus Rössler
Peter Pöchlauer
Michael Hartmann
Paul Alsters
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Patheon Austria GmbH and Co KG
Original Assignee
DSM Fine Chemicals Austria Nfg GmbH and Co KG
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Priority to EP02774014A priority Critical patent/EP1390336A1/fr
Publication of WO2002096849A1 publication Critical patent/WO2002096849A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B41/00—Formation or introduction of functional groups containing oxygen
    • C07B41/04—Formation or introduction of functional groups containing oxygen of ether, acetal or ketal groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B41/00—Formation or introduction of functional groups containing oxygen
    • C07B41/06—Formation or introduction of functional groups containing oxygen of carbonyl groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C201/00—Preparation of esters of nitric or nitrous acid or of compounds containing nitro or nitroso groups bound to a carbon skeleton
    • C07C201/06—Preparation of nitro compounds
    • C07C201/12—Preparation of nitro compounds by reactions not involving the formation of nitro groups
    • 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
    • C07C45/40—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with ozone; by ozonolysis
    • 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
    • C07C45/51—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition
    • C07C45/54—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition of compounds containing doubly bound oxygen atoms, e.g. esters
    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
    • C12P7/00—Preparation of oxygen-containing organic compounds
    • C12P7/24—Preparation of oxygen-containing organic compounds containing a carbonyl group

Definitions

  • Aromatic aldehydes and ketones such as benzaldehyde, p-tert-butylbenzaldehyde, anisaldehyde, 3-phenoxybenzaldehyde, acetophenone, etc., play in the chemical and pharmaceutical industry in various fields, such as the area of flavors and odorants, and crop protection - and pharmaceuticals sector, play an important role as intermediates with particularly high value creation potential.
  • the oxidation of alkyl aromatic compounds to obtain the aromatic carbonyl compounds is an important reaction in organic chemistry, since it enables the conversion of easily accessible or available organic substrates with limited reactivity into compounds with more reactive functional groups and thus with higher reactivity.
  • alkyl aromatic compounds are reacted with a peroxide in a solvent from the group of the carboxylic acids and their anhydrides using a cerium catalyst and in the presence of a bromide ion to give the corresponding aldehydes.
  • the percentage of aldehyde yield is still lower, at most 61%.
  • EP 0 721 442 also always receives by-products, such as the corresponding alcohol, the monobromide compound or the acetate, in large amounts.
  • by-products such as the corresponding alcohol, the monobromide compound or the acetate
  • manganese substituted polyoxometalates such as Lii2 [Mn “ 2 ZnW (ZnW9 ⁇ 3 4) 2] as a catalyst in the oxidation of alkyl aromatics, for example ethylbenzene, to ketones, for example acetophenone, with ozone in an aqueous medium at - 78
  • ° C provides the corresponding ketones with an up to 82% conversion in a yield of 85 mol%, 15 mol% of the corresponding alcohol be obtained as a by-product.
  • Ar is an aromatic or heteroaromatic ring of 5 or 6 or an aromatic or heteroaromatic ring system with up to 20 carbon atoms
  • Ar is optionally one or more times by C 1 -C 6 -alkyl or alkoxy, halogen, NO 2 , NR-
  • R 2 with R 1 and R 2 independently of one another are H or -CC alkyl, CN, OH, phenyl, keto groups, suiphonic acid groups, sulfonyl chloride, silyl radicals, siloxy or siloxane substituents or substituted with a -C 6 alkyl group, in which up to 2 carbon atoms can be replaced by a heteroatom, can be fused, n is 1 or 2, and R is hydrogen, CrC 2 o -alkyl or -alkenyl or phenyl, or together with Ar an optionally by C ⁇ - C- 6 alkyl or alkoxy, halogen, NO 2 , NR 1 R 2 , with
  • alkylaromatic compounds of the formula (I) are converted into the corresponding carbonyl compounds by catalytic oxidation.
  • Ar means an aromatic or heteroaromatic ring of 5 or 6 or an aromatic or heteroaromatic ring system with up to 20 carbon atoms. Examples include phenyl, naphthyl, anthracene, phenanthrene, indene, thiophene, pyrrole, furan, imidazole, pyridine, pyridazine, pyrimidine, pyrazine, quinoline, azepine, phenanthridine, isoquinoline, indole, dibenzothiophene, dibenzofuran, beta-carboline, indolizine , Carbazole, purine, pteridine, indazole, pyrrazole, 1, 2,3-triazole, 1, 2,4-triazole, tetrazole, oxozole, isoxazole, piperazine, dithiane, di
  • Ar is preferably phenyl, naphthyl, pyridine, imidazole and quinoline.
  • Ar can optionally be one or more times by CrC ⁇ alkyl or alkoxy, halogen, NO 2 , NR-
  • C 1 -C 6 -alkyl or -alkoxy are linear or branched alkyl or alkoxy groups, such as methyl, ethyl, n-propyl, i-propyl, n-butyl, tert-butyl, methoxy, ethoxy, propoxy, Butoxy, hexyloxy, etc. to understand.
  • Preferred are -C-alkyl and Ci-C 2 alkoxy radicals.
  • Halogen means fluorine, chlorine, bromine or iodine, with fluorine, chlorine and bromine being preferred.
  • NR ⁇ are to be understood as amine and substituted amines, where R 1 and R 2 independently of one another are H or C 1 -C 4 -alky! can mean. Both radicals are preferably R- and R 2 are H or CC 2 -alkyl. Examples of suitable silyl radicals are silyl, trimethylsilyl, phenyldimetylsilyl and di-tert-butylmethylsilyl.
  • Ar can optionally also be fused with a C 6 -C 6 -alkyl group in which up to 2 C atoms can be replaced by a hetero atom.
  • n means 1 if the C atom is part of a double bond; otherwise n means 2.
  • R can be hydrogen, C 1 -C 2 -alkyl or alkenyl, phenyl, benzyl, imidazoyl, indenyl,
  • C 1 -C 2 -alkyl or alkenyl radicals are to be understood as meaning linear, branched or cyclic alkyl or alkenyl radicals with up to 2 double bonds. Cr are preferred
  • C 1-10 alkyl or alkenyl radicals particularly preferably C 1 -C 6 alkyl or alkenyl radicals.
  • R can also, together with Ar, optionally by CrC ⁇ alkyl or alkoxy,
  • CN OH, phenyl, keto groups, suiphonic acid groups substituted ring system, which may contain one or more optionally substituted heteroatoms.
  • Examples of compounds of the formula (I) are toluene, 2-bromotoluene, 3-bromotoluene, 4-bromotoluene, 2, chlorotoluene, 3-chlorotoluene, 4-chlorotoluene, 2-fluorotoluene, 3-fluorotoluene, 4-fluorotoluene, 3,4 -Dichlorotoluene, 3,4-difluorotoluene, 4-tert-butyltoluene, ethylbenzene, o-nitro-toluene, m-nitrotoluene, p-trifluoromethyltoluene, 3-5-di- (trifluoromethyl) toluene, p-nitro-toluene, p -Toluidine, p-cumene, cresols, mono-, di- or trialkyl- or alkoxynaphthalenes
  • Suitable solvents are C 1 -C 6 mono- or dicarboxylic acids or their anhydrides, such as acetic acid, acetic anhydride, propionic acid or mixed anhydrides thereof, and solutions of anhydrides in other solvents, for example succinic anhydride.
  • Ci-C ⁇ -carboxylic acid esters such as ethyl acetate, isopropyl acetate, t-butyl acetate, n-butyl acetate, are preferably used as esters.
  • Suitable halogenated hydrocarbons are, for example, dichloromethane, 1,2-dichloroethane, chloroform or carbon tetrachloride.
  • C 1 -C 6 alcohols such as methanol, n-butanol, tert-butanol, amides, such as dimethylformamide, silicones and silicone oils and chemically inert high-boiling solvents, for example white oil.
  • amides such as dimethylformamide, silicones and silicone oils and chemically inert high-boiling solvents, for example white oil.
  • the solvents mentioned above can also be used as mixtures.
  • CrC 4 mono- or dicarboxylic acids or their anhydrides such as acetic acid, acetic anhydride, propionic acid or succinic anhydride, are preferred;
  • Ci-C 4 alcohols such as methanol, n-butanol, tert-butanol; or mixtures with water or chlorinated hydrocarbons.
  • Particularly preferred solvents are acetic acid, acetic anhydride, methanol, MeOH / H 2 O, n-butanol and acetic acid / dichloromethane.
  • Transition metal catalysts are used as the catalyst. Suitable transition metal catalysts are based on the elements from group 3B, such as Sc, Y, La, Ce, Sm or lanthanoids, Ac or other actinides, from group 4B (Ti, Zr, Hf), group 5B (V, Nb, Ta) , Group 6B (Cr, Mo, W), Group 7B (Mn, Tc, Re), Group 8 (Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt), Group 1 B (Cu, Ag, Au) and from Group 2B (e.g. Zn , Cd).
  • group 3B such as Sc, Y, La, Ce, Sm or lanthanoids, Ac or other actinides
  • group 4B Ti, Zr, Hf
  • group 5B V, Nb, Ta
  • Group 6B Cr, Mo, W
  • Group 7B Mn, Tc, Re
  • Group 8 Group 8 (Fe, Ru, Os, Co, Rh, Ir,
  • Catalysts are preferably used, the Sc, Sm or Y from the group 3B, La or Ce from the group of the lanthanides; Ti, Zr from group 4B, V or Ta from group 5B, Cr, Mo or W from group 6B, Mn or Re from group 7B, Fe, Co, Ni, Pd from group 8B or Cu from the group 1B included.
  • Catalysts which contain Sm, La, Ce, Ni, Co, V, Cr, Mn or Cu are particularly preferred.
  • the catalyst can be used as metal hydroxide, metal oxide, as organic salt, inorganic salt, etc. be used.
  • Hydroxides are, for example, Mn (OH) 2, MnO (OH), Fe (OH) 2 and Fe (OH) 3 .
  • Suitable oxides are, for example, S1TI 2 O 3 , TiO 2 , ZrO 2 , V 2 O 3 , V 2 O 5 , CrO, Cr 2 ⁇ 3 , M0O 3 , MnO, Mn 3 O 4 , Mn 2 O 3 , MnO 2 , Mn 2 O 7 , FeO, Fe 2 O 3 , Fe 3 O 4 , RuO 2 , RuO 4 , CoO, CoO 2 , C0 2 O 3 , Cu 2 O 3 , etc.
  • Organic salts are, for example formates, acetates, propionates, acetylacetonates te, benzoates, alcoholates, naphthenates, stearates, and other salts with C2-C2 0 fatty acids of Co, Mn, Ce, Ti, Zr, V, Cr, Mo, Fe, Ru , Ni, Pd, Cu and Zn.
  • Inorganic salts include, for example, nitrates, sulfates, phosphates, carbonates and halides of V, Co, Fe, Mn, Ni, Cu, etc
  • the catalyst can also be in the form of a complex, as described, for example, in EP-A1-0 824 962, as a 2-nucleus catalyst, with ligands or bridged, etc. be used.
  • the catalyst is an organic salt, e.g. Acetate, acetylacetonate, etc., and as an inorganic salt, e.g. Nitrate, etc. used.
  • the catalyst can be applied in solid form to a support. Suitable carriers are, for example, silica, zeolite, activated carbon, etc. or other porous supports.
  • catalyst mixtures of two or more catalysts can also be used.
  • the catalyst or the catalyst mixture is used in an amount of 0.001 mol% to 1 mol, preferably from 0.01 to 1 mol% and particularly preferably from 0.1 to 025 mol% per mol of substrate.
  • the catalytic oxidation is optionally carried out in the presence of an acid.
  • Strong acids such as H 2 SO, H 2 SO / SO 3 , HNO 3 and other mineral acids or trichloroacetic acid, trifluoroacetic acid, metanesulfonic acid or other sulfonic acids are suitable as acids.
  • the process according to the invention is preferably carried out in the presence of an acid, with H 2 SO being particularly preferred as the acid.
  • the amount of acid added is 0.001 mol to 1 mol, preferably 0.01 to 0.8 mol and particularly preferably 0.1 to 0.5 mol per mol of substrate.
  • Ozone serves as the oxidizing agent. Ozone is preferably used in an equimolar amount, based on the substrate. However, an excess of ozone can also be used.
  • the reaction temperature in the process according to the invention is between -70 and 100 ° C. or at the reflux temperature, preferably between -20 and 70 ° C. and particularly preferably between 0 and 30 ° C.
  • the substrate, the catalyst and, if appropriate, the acid are placed in the appropriate solvent and brought to the desired reaction temperature.
  • Ozone is then introduced into the reaction mixture until ozonolysis is complete. Any excess ozone remaining in the solvent is blown out with nitrogen.
  • the reaction mixture is then either evaporated to dryness or, if appropriate, concentrated by distilling off part of the solvent and the remaining reaction solution in water at a temperature of 5 to 100 ° C., preferably 10 to 100 ° C. and particularly preferably 15 to 100 ° C. brought in.
  • the reaction product is then isolated, depending on its state of matter, by customary methods, such as extraction, distillation, chromatography, etc. in the case of liquid products or filtration, centrifugation, sublimation, etc. in the case of solid products.
  • this group In order to obtain the desired aldehyde or ketone, this group, known as the carbonyl protecting group, must be split off. This can be done in a known way using various methods. Suitable methods are the thermal route, by heating, the chemical route and the enzymatic route.
  • the reaction solution obtained by introducing the reaction mixture into water is used for a few minutes to several hours, preferably for 10 minutes to 12 hours, particularly preferably for 20 minutes to 6 hours and very particularly preferably for 30 minutes to 2 hours, heated to 50 to 100 ° C at normal pressure, or at elevated pressure of over 1 bar to 200 bar, preferably 2 to 10 bar, in a tubular reactor, autoclave, pressure reactor, loop reactor or other for work under pressure suitable apparatus to a temperature above 100 ° C, preferably heated to 110 to 150 ° C and then, after cooling, the desired aldehyde or the ketone, depending on the state of matter, isolated by the methods listed above or by steam distillation.
  • the chemical cleavage takes place, as from the prior art, for example from Greene, fury; Protective Groups in Organic Synthesis, 3rd Edition, 1998, is known by acidic or basic hydrolysis, for example using mineral acids, acidic ion exchangers, organic acids, silica gel, carbonates, sodium or potassium hydroxide solution, basic ion exchangers, etc.
  • the enzymatic variant is also carried out analogously to the prior art, for example analogously to Greene, rage; Protective Groups in Organic Synthesis, 3rd Edition, 1998 or analogous to Tetrahedron Letters, Vol. 38, No. 46, pp. 8109-8112 (1997).
  • the acylal can also be isolated as such, depending on the state of matter, by the usual methods above, such as filtration, extraction, etc.
  • the acylal is a storage-stable compound, so it is advantageous, if the actual end product is not required immediately, to store it in the form of the corresponding acylal and only to remove the protective group if necessary.
  • Another possibility is to convert the acylal into another protective group, for example by reaction with an alcohol or with S compounds, which in some cases gives very valuable intermediates in the synthesis of pharmaceuticals.
  • reaction with methanol or ethanol gives the corresponding dialkoxy compounds.
  • These compounds can also be used for better storage of the actual end product, the corresponding aldehyde or ketone again being obtained if necessary by the cleavage methods described above.
  • the desired aromatic aldehydes and ketones are obtained in high yields in a simple manner by the process according to the invention, with a significantly lower by-product content compared to the prior art.
  • the process according to the invention is particularly suitable for the preparation of benzaldehydes.
  • the mother liquor was mixed with 200 ml of saturated NaCl solution and extracted twice with 200 ml of dichloromethane.
  • the ozone present in the solvent was blown out with nitrogen. Thereafter, 100 ml of acetic anhydride were distilled off and the remaining 100 ml of the reaction solution was dropped into 500 ml of water at room temperature and extracted twice with dichloromethane. The combined organic extracts were dried over sodium sulfate and evaporated.
  • Example 8 4-Fe-butylbenzaldehyde diacetate (4-Fe / f-Bi-tylbenzaldehyde acylal)
  • the ozone present in the solvent was blown out with nitrogen. Thereafter, 100 ml of acetic anhydride was distilled off and the remaining 100 ml of the reaction solution was introduced into 200 ml of water at room temperature. The crystalline precipitate was filtered off, the mother liquor was extracted three times with 50 ml of dichloromethane each time and the combined organic extracts were dried over sodium sulfate and evaporated.
  • Example 16 Chemical conversion of p-bromobenzaldehyde diacetate to p-bromobenzaldehyde
  • Example 17 Enzymatic conversion of p-bromobenzaldehyde diacetate to p-bromobenzaldehyde
  • the diacylal to be deprotected was suspended in a buffer solution or in pure water in a 20 ml reaction vessel and a defined amount of enzyme was added at 25 ° C.
  • the solution was analyzed by gas chromatography (see table)

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Abstract

L'invention concerne un procédé pour réaliser l'oxydation catalytique de composés aromatiques alkylés de formule (I) : Ar-C(H)n-R, afin de permettre l'obtention d'aldéhydes et de cétones aromatiques correspondants. Dans ladite formule, Ar représente un cycle à 5 ou 6 chaînons, aromatique ou hétéroaromatique, éventuellement substitué, ou un système cyclique comportant au maximum 20 atomes de C, Ar pouvant éventuellement être condensé avec un groupe alkyle C1-C6, dans lequel au maximum 2 atomes de C peuvent être remplacés par un hétéroatome ; n vaut 1 ou 2 ; et R représente hydrogène, alkyle C1-C20 ou alcényle C1-C20 ou phényle, ou forme conjointement avec Ar un système cyclique éventuellement substitué qui peut contenir un ou plusieurs hétéroatomes éventuellement substitués. Ce procédé consiste à oxyder un composé de formule (I) dans un solvant avec de l'ozone en présence d'un catalyseur de métal de transition et éventuellement en présence d'un acide à une température comprise entre 70 DEG C et 100 DEG C ou dans des conditions de reflux, pour permettre l'obtention de l'aldéhyde ou de la cétone correspondant(e).
PCT/EP2002/004795 2001-05-25 2002-05-02 Procede pour produire des aldehydes et des cetones aromatiques par oxydation catalytique de composes aromatiques alkyles Ceased WO2002096849A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP02774014A EP1390336A1 (fr) 2001-05-25 2002-05-02 Procede pour produire des aldehydes et des cetones aromatiques par oxydation catalytique de composes aromatiques alkyles

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
AT8252001A AT410441B (de) 2001-05-25 2001-05-25 Verfahren zur herstellung von aromatischen aldehyden und ketonen durch katalytische oxidation alkylaromatischer verbindungen
ATA825/2001 2001-05-25

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1362840A1 (fr) * 2002-05-15 2003-11-19 DSM Fine Chemicals Austria Nfg GmbH & Co KG Procédé de préparation des acides carboxyliques aromatiques et hétéroaromatiques par ozonolyse catalytique
WO2005090289A1 (fr) * 2004-03-23 2005-09-29 Central Glass Company, Limited Dérivé de 3-formyl-5-trifluorométhylbenzonitrile et procédé pour fabriquer celui-ci
WO2007129745A1 (fr) 2006-05-09 2007-11-15 Daiichi Sankyo Company, Limited Derive acide carboxylique inferieur d'heteroarylamide
TWI508944B (zh) * 2014-10-13 2015-11-21 Nat Univ Tsing Hua 以臭氧、單重態氧原子自由基或氫氧自由基製備羧酸或酮類之方法

Families Citing this family (1)

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Publication number Priority date Publication date Assignee Title
DK2222168T3 (en) 2007-11-26 2018-12-03 Merial Inc SOLUTION SYSTEMS FOR POUR-ON FORMULAS TO FIGHT PARASITES

Citations (1)

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Publication number Priority date Publication date Assignee Title
GB616330A (en) * 1946-08-26 1949-01-19 George Aubrey Baker Improvements in the manufacture of aryl alkyl ketones and carbinols

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Publication number Priority date Publication date Assignee Title
GB762738A (en) * 1954-01-08 1956-12-05 Dow Chemical Co Catalytic oxidation of aromatic carboxylic acids to phenols
JPS6081139A (ja) * 1983-10-11 1985-05-09 Agency Of Ind Science & Technol シクロペンタノンの製造方法
GB9319945D0 (en) * 1993-09-28 1993-11-17 Solvay Interox Ltd Oxidation of alkylaromatic compounds

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB616330A (en) * 1946-08-26 1949-01-19 George Aubrey Baker Improvements in the manufacture of aryl alkyl ketones and carbinols

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
ALLAN S. HAY ET AL.: "Catalytic Oxidation of Hydrocarbons. Initiated by Ozone", J. ORG. CHEM., vol. 25, 1960, pages 616 - 7, XP002218948 *

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1362840A1 (fr) * 2002-05-15 2003-11-19 DSM Fine Chemicals Austria Nfg GmbH & Co KG Procédé de préparation des acides carboxyliques aromatiques et hétéroaromatiques par ozonolyse catalytique
WO2005090289A1 (fr) * 2004-03-23 2005-09-29 Central Glass Company, Limited Dérivé de 3-formyl-5-trifluorométhylbenzonitrile et procédé pour fabriquer celui-ci
WO2007129745A1 (fr) 2006-05-09 2007-11-15 Daiichi Sankyo Company, Limited Derive acide carboxylique inferieur d'heteroarylamide
TWI508944B (zh) * 2014-10-13 2015-11-21 Nat Univ Tsing Hua 以臭氧、單重態氧原子自由基或氫氧自由基製備羧酸或酮類之方法
US9637438B2 (en) 2014-10-13 2017-05-02 National Tsing Hua University Preparation method of carboxylic acids or ketones using ozone, singlet state-oxygen atom or hydroxyl free radical

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EP1390336A1 (fr) 2004-02-25
AT410441B (de) 2003-04-25
ATA8252001A (de) 2002-09-15

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