EP0000542B1 - Procédé de préparation de trifluorométhylphénols - Google Patents

Procédé de préparation de trifluorométhylphénols Download PDF

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Publication number
EP0000542B1
EP0000542B1 EP78100436A EP78100436A EP0000542B1 EP 0000542 B1 EP0000542 B1 EP 0000542B1 EP 78100436 A EP78100436 A EP 78100436A EP 78100436 A EP78100436 A EP 78100436A EP 0000542 B1 EP0000542 B1 EP 0000542B1
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EP
European Patent Office
Prior art keywords
process according
nitro
employed
formula
alkali metal
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EP78100436A
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German (de)
English (en)
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EP0000542A1 (fr
Inventor
Albrecht Dr. Marhold
Erich Dr. Klauke
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Bayer AG
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Bayer AG
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    • 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

Definitions

  • the invention relates to a process for the preparation of phenols having a trifluoromethyl group.
  • trifluoromethylphenols are obtained by cleaving the corresponding methoxy compounds with pyridine hydrochloride at 210 ° C. (J. org. Chem. 27, 4660 (1962): in this process, the methoxy compounds are prepared from chloronitrobenzotrifluorides in a preceding process step.
  • Halogens (X) can be fluorine, chlorine, bromine or iodine, preferably fluorine or chlorine.
  • Halogen atom (Y) may be, for example, fluorine, chlorine, bromine or iodine, preferably chlorine or bromine.
  • the alkoxy group (Y) preferably contains alkyl radicals having 1 to 4 carbon atoms, for example the methyl, ethyl, propyl, isopropyl, butyl or tert-butyl radical.
  • Alkonols with a lower unbranched or branched alkyl radical can be used as solvents for the process according to the invention.
  • Alcohols whose unbranched or branched alkyl radical has 1 to 4 carbon atoms such as methanol, ethanol, propanol, isopropanol, the various isomeric butanols, glycol and glycol monomethyl ether, are preferred.
  • the amount of solvent can vary within wide limits, for example 1 to 20 parts by weight, preferably 2 to 8 parts by weight, of solvent can be used per 1 part by weight of a compound of the formula (I).
  • Sodium or potassium hydroxide are preferably used as alkali metal hydroxides for the process according to the invention. They are generally used in the form of their aqueous solutions which contain, for example, 30-50% by weight of alkali metal hydroxide. However, the sodium or potassium hydroxide can also be added in solid form to the aqueous alcoholic solution.
  • the alkali metal hydroxides are generally used in excess, the use of about three times the molar amount based on the conversion of the halogen atom to the phenolic hydroxyl group is particularly advantageous.
  • the water content of the reaction solution can vary within wide limits. In general, it can be about 20 to 25% by weight.
  • the radicals R 4 to R 7 can be low-molecular or high-molecular organic radicals.
  • Optionally substituted alkyl radicals, cycloalkyl radicals, aralkyl radicals or aryl radicals may be mentioned as low molecular weight organic radicals.
  • Two of the radicals R 4 to R 7 can also form a heterocycle together with the central atom Z and optionally further heteroatoms.
  • the optionally substituted or branched alkyl radicals can especially those with 1-18 Carbon atoms, preferably having 1-12 carbon atoms, such as the methyl, ethyl, isomeric propyl, butyl, octyl, decyl or dodecyl radicals.
  • the cycloalkyl radicals can be cyclopentyl and in particular cyclohexyl radicals which are optionally substituted by C 1 -C 4 -alkyl radicals.
  • the aralkyl radicals can optionally be benzyl radicals substituted by C i -c 4- alkyl radicals, methoxy groups or halogen atoms.
  • the aryl radicals can be phenyl radicals which are optionally substituted by C 1 -C 4 -alkyl radicals, methoxy groups, ethoxy groups or halogen atoms.
  • the 5- and 6-membered heterocycles may be mentioned, for example the pyrrolidine ring, the piperidine ring or the morpholine ring.
  • polystyrene which may be crosslinked by divinylbenzene.
  • the total number of carbon atoms of all radicals R 4 to R 7 is at least six for the process according to the invention.
  • the maximum number of all carbon atoms in a polymeric organic radical can be very large.
  • the preferred total number of carbon atoms of all low-molecular radicals R 4 to R 7 is 8 to 25.
  • Preferred anions A are the chloride, bromide and hydroxide anion.
  • Examples of the preferred quaternary ammonium or phosphonium salts are: tetraethylammonium chloride, tetrabutylammonium bromide, triethylbenzylammonium hydroxide, benzyldimethyldodecylammonium chloride, dibutylpiperidiniumbromide, methyltrioctylammoniumchloride, dimethylbenzylpidylphenyl-methyldylylphenyl-methylphenyl-methyl-phenyl methyl-piperdinium hydroxide, triethyl-phenyl-ammonium chloride, dodecyl-trimethyl-ammonium hydroxide, cyclohexyldodecyl-dimethyl-ammonium chloride, methyl-ethyl-piperidinium bromide, triphenyl-benzyl-phosphonium bromide, tetrabutyl-phosphonium chloride,
  • Quaternary ammonium compounds in which one of the radicals R 4 to R 7 is a polymeric radical can be, for example, ion exchangers based on styrene and generally 2 mol% of divinylbenzene as crosslinking agents which carry quaternary ammonium groups.
  • the amounts of the quaternary onium salt used can vary from 1 to 20% by weight and are generally about 5 to 10% by weight, based on the starting compound.
  • phase transition catalysts in multiphase systems and can be prepared by known processes (Houben-Weyl, 4th ed. Stuttgart 1958, volume XI, 2, p. 587 and volume XIV, 2nd p. 750).
  • the process according to the invention can be carried out in the temperature range from about 0 to about 80 ° C., preferably from about 50 to 75 ° C.
  • the alkyl radicals R 12 of these alkoxy compounds are determined by the alcohol used as solvent; when using methanol, a methoxy compound is obtained.
  • alkoxy compounds are known (J. Org. Chem. 26, 2707 (1961)) and can be prepared, for example, by reacting an organically bonded halogen atom with sodium methylate or with methanolic potassium hydroxide.
  • the process according to the invention has the advantage of being simple to carry out and of leading to the desired phenols in one step.
  • the quaternary onium salts of the formula (IV) are known as phase transition catalysts in systems with two immiscible liquid phases (DT-OS 2 634 419).
  • the method according to the invention is carried out with quaternary onium compounds in a system with only one liquid phase.
  • the trifluoromethylphenols are intermediate products for the production of crop protection agents, in particular herbicides (DT-OS 2311 638, DT-OS 1 944 335).
  • a trifluoromethylphenol of the formula VI can be reacted with p-nitrochlorobenzene in the presence of potassium m-methylate to give trifluoromethyl-nitrodiphenyl ether.
  • Herbicides from new trifluoromethylphenols of the formula VII show improved activity compared to the known herbicides.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Claims (11)

1. Procédé de production de trifluorométhylphénols, caractérisé en ce qu'on fait réagir des composés de formule:
Figure imgb0019
dans laquelle:
X est un halogène,
R1,R2 R3 représentent de l'hydrogène ou un groupe trifluorométhyle, nitro, alkylsulfonyle, arylsulfone, carboxyle ou ester d'acide carboxylique, et
Y est de l'hydrogène, un halogène ou un groupe alkoxy,

l'un des substituants R1, R2 et R3 représentant un groupe trifluorométhyle et au moins un autre étant différent d'un atome d'hydrogène, en solution alcoolique avec un hydroxyde alcalin aqueux en excès en présence de sels d'onium quaternaire.
2. Procédé suivant la revendication 1, caractérisé en ce qu'on opère en présence d'un sel d'onium quaternaire de formule:
Figure imgb0020
dans laquelle:
Z est un atome du cinquième groupe du Système Périodique,
R4 à R7 représentent, indépendamment l'un de l'autre, un groupe alkyle, cyclo-alkyle, aralkyle ou aryle éventuellement substitué ou deux des restes R4 à R7 forment un hétérocycle avec l'atome central Z et, le cas échéant, avec d'autres hétéro-atomes, les restes R4 à R7 comprenant ensemble au moins 6 atomes de carbone, et
A est un anion chlorure, bromure ou hydroxyde.
3. Procédé suivant l'une des revendications 1 et 2, caractérisé en ce que le sel d'onium quaternaire est un sel d'ammonium ou phosphonium quaternaire dont les substituants totalisent 8 à 25 atomes de carbone.
4. Procédé suivant l'une des revendications 1 et 2, caractérisé en ce qu'on utilise comme sel d'ammonium quaternaire un échangeur d'ions à base de styrène avec 2 moles % de divinylbenzène comme agent de réticulation, qui porte des groupes ammonium quaternaire.
5. Procédé suivant les revendications 1 à 4, caractérisé en ce qu'on utilise le sel d'onium quaternaire en une quantité de 1 à 20% en poids par rapport à l'halogénobenzotrifluorure.
6. Procédé suivant les revendications 1 à 5, caractérisé en ce que le sel d'onium quaternaire est utilisé en une quantité de 5 à 10% en poids par rapport à l'halogénobenzotrifluorure.
7. Procédé suivant les revendications 1 à 6, caractérisé en ce qu'on utilise comme solvant alcoolique des alcools portant un reste alkyle inférieur non ramifié ou ramifié.
8. Procédé suivant les revendications 1 à 7, caractérisé en ce qu'on utilise l'hydroxyde de métal alcalin en une quantité molaire triple par rapport à l'halogénobenzotrifluorure.
9. Procédé suivant les revendications 1 à 8, caractérisé en ce qu'on utilise comme hydroxyde de métal alcalin l'hydroxyde de sodium ou l'hydroxyde de potassium.
10. Procédé suivant les revendications 1 à 9, caractérisé en ce qu'on conduit la réaction dans la plage de températures de 0 à 80°C.
11. Procédé suivant la revendication 1, caractérisé en ce que,
a) on fait réagir des composés de formule:
Figure imgb0021
dans laquelle:
X, Y, R1, R2 et R3 ont la définition donnée ci-dessus, en présence d'un alcool portant un reste alkyle inférieur non ramifié ou ramifié, servant de solvant, avec un hydroxyde alcalin aqueux en excès en présence de sels d'onium quaternaire à des températures comprises entre 15 et 35°C, et
b) on fait réagir les composés ainsi produits, de formule:
Figure imgb0022
dans laquelle:
Y, R', R2 et R3 ont la définition donnée ci-dessus, et
R12 désigne un reste alkyle inférieur non ramifié ou ramifié,

en solution alcoolique avec un hydroxyde alcalin aqueux en excès en présence de sels d'onium quaternaire.
EP78100436A 1977-07-26 1978-07-19 Procédé de préparation de trifluorométhylphénols Expired EP0000542B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE2733682 1977-07-26
DE19772733682 DE2733682A1 (de) 1977-07-26 1977-07-26 Verfahren zur herstellung von trifluormethylphenolen

Publications (2)

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EP0000542A1 EP0000542A1 (fr) 1979-02-07
EP0000542B1 true EP0000542B1 (fr) 1981-07-15

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EP78100436A Expired EP0000542B1 (fr) 1977-07-26 1978-07-19 Procédé de préparation de trifluorométhylphénols

Country Status (7)

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US (1) US4225731A (fr)
EP (1) EP0000542B1 (fr)
JP (1) JPS5424839A (fr)
DE (2) DE2733682A1 (fr)
DK (1) DK154949C (fr)
IL (1) IL55209A (fr)
IT (1) IT1105942B (fr)

Families Citing this family (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4400552A (en) * 1980-04-21 1983-08-23 The Franklin Institute Method for decomposition of halogenated organic compounds
US4460797A (en) * 1981-03-05 1984-07-17 The Franklin Institute Method for decomposition of halogenated organic compounds
DE3120912A1 (de) * 1981-05-26 1982-12-16 Hoechst Ag, 6000 Frankfurt Verfahren zur herstellung von p-nitrophenetol
FR2529197A1 (fr) * 1982-06-29 1983-12-30 Rhone Poulenc Agrochimie Procede de preparation de phenates substitues par des groupes halogenes ou des phenols correspondants
US4417977A (en) * 1982-09-30 1983-11-29 The Franklin Institute Removal of PCBS and other halogenated organic compounds from organic fluids
US4602994A (en) * 1982-09-30 1986-07-29 The Franklin Institute Removal of PCBs and other halogenated organic compounds from organic fluids
HU190439B (en) * 1983-02-03 1986-09-29 Budapesti Vegyimuevek,Hu Herbicidal, akaricidal and plant growth regulating compsitions comprising 2-/trifluoromethyl/-4,6-dinitrophenol or its salts as active substance and process for preparing the active substances
GB8708517D0 (en) * 1987-04-09 1987-05-13 Shell Int Research Preparation of fluorophenols
DE3712817A1 (de) * 1987-04-15 1988-10-27 Bayer Ag Verwendung von fluormethylphenolen als loesungsmittel fuer lc-polymere, und neue fluormethylphenole
ES2083048T3 (es) * 1991-10-09 1996-04-01 Hoechst Ag Procedimiento para fabricar 2-nitro-5-fluoro- o bien -5-cloro-fenol.

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB718779A (en) * 1952-01-05 1954-11-17 Pechney Cie De Prod Chim Et El Process for manufacturing pentachlorophenol and alkali pentachlorophenates
US2872461A (en) * 1954-10-21 1959-02-03 Schering Ag Process of producing chloranil
US2950325A (en) * 1958-06-06 1960-08-23 Dow Chemical Co Process for making fluorophenols
NL295899A (fr) * 1962-07-30
FR1469596A (fr) * 1966-01-06 1967-02-17 Saint Gobain Procédé de préparation du para-trifluorméthylphénol
US3813446A (en) * 1968-06-24 1974-05-28 Sherwin Williams Co Production of trifluoromethylnitrophenols and related compounds
US3943180A (en) * 1972-02-29 1976-03-09 Bayer Aktiengesellschaft 2,4-Bis-(trifluoromethyl)-6-nitrophenol compounds and herbicidal compositions

Also Published As

Publication number Publication date
IL55209A0 (en) 1978-09-29
JPS6256850B2 (fr) 1987-11-27
IT7850434A0 (it) 1978-07-24
JPS5424839A (en) 1979-02-24
DK154949C (da) 1989-05-29
DK154949B (da) 1989-01-09
IT1105942B (it) 1985-11-11
DE2733682A1 (de) 1979-02-08
IL55209A (en) 1983-02-23
DE2860838D1 (en) 1981-10-22
DK330178A (da) 1979-01-27
US4225731A (en) 1980-09-30
EP0000542A1 (fr) 1979-02-07

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