FR2589147A1 - Process for the preparation of perfluoroalkylated phenol derivatives - Google Patents
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- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D213/62—Oxygen or sulfur atoms
- C07D213/63—One oxygen atom
- C07D213/64—One oxygen atom attached in position 2 or 6
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- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/26—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton
- C07C17/32—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton by introduction of halogenated alkyl groups into ring compounds
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- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/11—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions increasing the number of carbon atoms
- C07C37/18—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions increasing the number of carbon atoms by condensation involving halogen atoms of halogenated compounds
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- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/18—Preparation of ethers by reactions not forming ether-oxygen bonds
- C07C41/30—Preparation of ethers by reactions not forming ether-oxygen bonds by increasing the number of carbon atoms, e.g. by oligomerisation
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
- C07C67/333—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton
- C07C67/343—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
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- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/24—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D213/26—Radicals substituted by halogen atoms or nitro radicals
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- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D213/72—Nitrogen atoms
- C07D213/73—Unsubstituted amino or imino radicals
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Abstract
Description
PROCEDE DE PREPARATION DE DERIVES PHENOLIQUES PERFLUOROALKYLES
La présente invention concerne un procédé de préparation de dérivés phénoliques perfluoroalkylés. Elle concerne plus particu lièrement un procédé de perfluoroalkylation de dérivés phénoliques par des-halogénures de perfluoroalkyle.PROCESS FOR THE PREPARATION OF PERFLUOROALKYL PHENOLIC DERIVATIVES
The present invention relates to a process for the preparation of perfluoroalkylated phenolic derivatives. It relates more particularly to a process for perfluoroalkylation of phenolic derivatives by perfluoroalkyl halides.
I1 est connu, d'après J. FUCHIKAMI, I. OJIMA (J. Fluorine
Chemistry 1983, 22, 541) de perfluorer des phénols et leurs éthers par des iodures ou des bromures de perfluoroalkyle dont la channe alkyle contient au moins trois atomes de carbone en présence de cuivre métallique comme catalyseur. La trifluorométhylation des phénols et de leurs dérivés n'est pas décrite.It is known, according to J. FUCHIKAMI, I. OJIMA (J. Fluorine
Chemistry 1983, 22, 541) of perfluorinating phenols and their ethers by iodides or perfluoroalkyl bromides in which the alkyl chain contains at least three carbon atoms in the presence of metallic copper as catalyst. The trifluoromethylation of phenols and their derivatives is not described.
I1 est également connu d'après le brevet européen NO 114.359 de perfluoroalkyler des dérivés aromatiques et en particulier l'anisole (exemple 9) à l'aide dtiodure de perfluoroalkyle à longue chaîne, pendant 30 heures à 1700C et en présence d'un catalyseur à base de ruthénium. La trifluorométhylation n1 est jamais décrite dans ce brevet comme dans l'article précédent. It is also known from European Patent No. 114,359 to perfluoroalkylate aromatic derivatives and in particular anisole (Example 9) using perfluoroalkyl long chain iodide for 30 hours at 1700C and in the presence of a catalyst based on ruthenium. Trifluoromethylation n1 is never described in this patent as in the previous article.
L'iodure de trifluorométhyle tétant pas industriel, cette méthode de perfluoroalkylation n'est pas envisageable. Since trifluoromethyl iodide is not industrial, this perfluoroalkylation method cannot be envisaged.
Aucun autre procédé de l'art antérieur ne décrit de méthodes de perfluoroalkylation de dérivés phénoliques. Les procédés classiques de perfluoroalkylation tels que ceux décrits dans le brevet
EP 8453 ne sont pas applicables aux phénols car on obtient alors une perfluoroalkylation du groupe hydroxyle et non du noyau aromatique.No other process of the prior art describes methods of perfluoroalkylation of phenolic derivatives. Conventional perfluoroalkylation processes such as those described in the patent
EP 8453 are not applicable to phenols because one then obtains a perfluoroalkylation of the hydroxyl group and not of the aromatic ring.
La présente invention a su vaincre ces problèmes techniques et a pour objet un procédé de préparation de dérivés phénoliques perfluoroalkylés caractérisé en ce que, dans une première étape, on met en présence un dérivé phénolique, du dioxyde de soufre, un métal choisi parmi le zinc, l'aluminium, le manganèse, le cadmium, le fer, dans un solvant aprotique polaire ; dans une deuxième étape, on ajoute un bromure ou un iodure de perfluoroalkyle éventuellement en mélange avec du dioxyde de soufre. The present invention has overcome these technical problems and relates to a process for the preparation of perfluoroalkylated phenolic derivatives, characterized in that, in a first step, a phenolic derivative, sulfur dioxide, a metal chosen from zinc, is brought into contact , aluminum, manganese, cadmium, iron, in a polar aprotic solvent; in a second step, a perfluoroalkyl bromide or iodide is added, optionally in admixture with sulfur dioxide.
On entend au sens de la présente invention par dérivés phénoliques tout composé répondant à la formule générale (I)
R-Ar+O-Rl)n (I) dans laquelle
- Ar représente un radical aromatique mono ou polycyclique,
hétérocyclique,
- R représente au moins un substituant choisi parmi
I'hydrogène, les radicaux alkyles linéaires, ramifiés,
cycliques saturés ou insaturés, halogéno, éther, alcoxy,
aryloxy, alkylthio, arylthio, amino, carboxylate, acyloxy,
fluoroalkyl, fluoroalcoxy, fluoroalkylthio, ester, amido,
nitrile, acide.For the purposes of the present invention, the term “phenolic derivatives” means any compound corresponding to the general formula (I)
R-Ar + O-Rl) n (I) in which
- Ar represents a mono or polycyclic aromatic radical,
heterocyclic,
- R represents at least one substituent chosen from
Hydrogen, linear, branched alkyl radicals,
saturated or unsaturated cyclics, halo, ether, alkoxy,
aryloxy, alkylthio, arylthio, amino, carboxylate, acyloxy,
fluoroalkyl, fluoroalkoxy, fluoroalkylthio, ester, amido,
nitrile, acid.
- R1 représente l'hydrogène, un groupe alkyle contenant 1 à 12
atomes de carbone éventuellement substitué, un groupe aryle
éventuellement substitué et lorsque R est un groupe amino, R
représente lthydrogène. - R1 represents hydrogen, an alkyl group containing 1 to 12
optionally substituted carbon atoms, an aryl group
optionally substituted and when R is an amino group, R
represents hydrogen.
- n est un nombre entier égal à 1,2 ou 3. - n is an integer equal to 1,2 or 3.
Un des avantages particuliers de l'invention est l'utilisation des dérivés phénoliques de formule (I) dans lesquels Ar représente un radical aromatique monocyclique et R1 représente l'hydrogène. One of the particular advantages of the invention is the use of phenolic derivatives of formula (I) in which Ar represents a monocyclic aromatic radical and R1 represents hydrogen.
Parmi les dérivés phénoliques utilisés dans le procédé de l'invention, on peut citer, mais de façon non limitative : les phénols, les crésols, les phénylphénols, les chlorophénols, les aminophénols, les anisoles, les diphényléthers, les méthoxyphénols, les dihydroxybenzènes. Among the phenolic derivatives used in the process of the invention, there may be mentioned, but not limited to: phenols, cresols, phenylphenols, chlorophenols, aminophenols, anisoles, diphenyl ethers, methoxyphenols, dihydroxybenzenes.
Selon le procédé de l'invention, le bromure ou l'iodure de perfluoroalkyle répond de préférence à la formule générale (II) suivante
CF 2n + 1 (II) dans laquelle
- n est un nombre entier compris entre 1 et 12
- X représente Br ou I.According to the process of the invention, the perfluoroalkyl bromide or iodide preferably corresponds to the following general formula (II)
CF 2n + 1 (II) in which
- n is an integer between 1 and 12
- X represents Br or I.
D'un point de vue économique il est préférable d'utiliser, lorsque n est égal à 1, le bromure de trifluorométhyle et, lorsque n est supérieur à 1, les iodures de perfluoroalkyle. From an economic point of view it is preferable to use, when n is equal to 1, trifluoromethyl bromide and, when n is greater than 1, perfluoroalkyl iodides.
En effet, le bromure de trifluorométhyle est un gaz extincteur (M.R.C."GERSTENBERGER, A. HAAS Angew. Chem. Int." Ed. 1981, 20, 647) qui est un produit industriel fabriqué à large échelle donc d'un coût tout à fait accessible pour l'industrie. L'iodure de trifluorométhyle n'étant pas industriel n'est disponible qu'à un prix qui le rend tout à fait inutilisable. Par contre, dès que la chalne alkyle a au moins 2 atomes de carbone, les iodures de perfluoroalkyle se présentent sur le marché à des prix nettement inférieurs à ceux de leurs homologues bromés. Indeed, trifluoromethyl bromide is an extinguishing gas (MRC "GERSTENBERGER, A. HAAS Angew. Chem. Int." Ed. 1981, 20, 647) which is an industrial product manufactured on a large scale therefore of a cost quite made accessible for industry. The non-industrial trifluoromethyl iodide is only available at a price which makes it completely unusable. On the other hand, as soon as the alkyl chain has at least 2 carbon atoms, perfluoroalkyl iodides appear on the market at prices much lower than those of their brominated counterparts.
Parmi les ne taux, il est avantageux de choisir le zinc, d'un point de vue économique. Among the ne rates, it is advantageous to choose zinc, from an economic point of view.
Le métal est avantageusement utilisé sous forme dispersée de fanon à assurer le meilleur contact avec les gaz mis en oeuvre dans le procédé de l'invention. La forme et la dimension des particules de métal seront adaptées par l'homme de l'art à la réactivité des produits mis en oeuvre. The metal is advantageously used in the dispersed form of baleen to ensure the best contact with the gases used in the process of the invention. The shape and size of the metal particles will be adapted by those skilled in the art to the reactivity of the products used.
Le solvant choisi doit, autant que possible, permettre de solubiliser le dioxyde de soufre et lthalogénure de perfluoroalkyle. The solvent chosen must, as far as possible, make it possible to dissolve the sulfur dioxide and the perfluoroalkyl halide.
Répondent à cette condition, les solvants aprotiques polaires et parmi eux préférentiellement
- l'acétonitrile
- le diméthylformamide (D.M.F.)
- le diméthylsulfoxide (D.M.S.O,)
- le diméthylacétamide (D.M.A.)
- lthexaméthylphosphoramide (H.N.P.A.)
- la N-méthylpyrrolidone (N.M.P.)
Le diméthylformamide et le diméthylsulfoxide sont utilisés encore plus préférentiellement.Meet this condition, the polar aprotic solvents and among them preferentially
- acetonitrile
- dimethylformamide (DMF)
- dimethylsulfoxide (DMSO,)
- dimethylacetamide (DMA)
- lthexamethylphosphoramide (HNPA)
- N-methylpyrrolidone (NMP)
Dimethylformamide and dimethylsulfoxide are used even more preferably.
Pour une mise en oeuvre plus rapide du procédé, on préfère ajouter, lors de la première étape, une base organique et/ou minérale. Parmi les bases minérales, on peut citer notamment la soude, la potasse, la chaux, les métabisulfites alcalins. On préfère utiliser le métabisulfite de sodium. For faster implementation of the process, it is preferable to add, during the first step, an organic and / or mineral base. Among the mineral bases, there may be mentioned in particular soda, potash, lime, alkali metabisulfites. It is preferred to use sodium metabisulfite.
Parmi les bases organiques, on peut citer les pyridines et plus particulièrement la pyridine et les méthylpyridines. Among the organic bases, mention may be made of pyridines and more particularly pyridine and methylpyridines.
Selon un mode tout à fait privilégié de mise en oeuvre de l'invention, on utilise un rapport molaire du métal au dérivé phénolique compris entre 0,05 et 1 et de préférence compris entre 0,10 et 0,20 ; un rapport molaire de l'halogénure de perfluoroalkyle au dérivé phénolique, de préférence supérieur ou égal à 1. Si l'halogénure de perfluoroalkyle est mis en excès et que l'halogènure utilisé est le bromure de- trifluorométhyle, celui-ci sera aisément recyclé car il se présente sous forme gazeuse. According to a completely privileged mode of implementation of the invention, a molar ratio of the metal to the phenolic derivative is used between 0.05 and 1 and preferably between 0.10 and 0.20; a molar ratio of the perfluoroalkyl halide to the phenolic derivative, preferably greater than or equal to 1. If the perfluoroalkyl halide is put in excess and the halide used is trifluoromethyl bromide, this will be easily recycled because it is in gaseous form.
Le rapport molaire du dioxyde de soufre au dérivé phénolique mis en oeuvre est de préférence compris entre 0,05 et 1,5. The molar ratio of sulfur dioxide to the phenolic derivative used is preferably between 0.05 and 1.5.
Selon une méthode de mise en oeuvre avantageuse de l'invention, on utilise une base organique et/ou minérale. Lorsqu'on met en oeuvre une base minérale, on préfère l'utiliser selon un rapport molaire base minérale au dérivé phénolique compris entre 0,4 et 1 et lorsqu'on met en oeuvre une pyridine, on préfère l'utiliser selon un rapport molaire pyridine au dérivé phénolique compris entre 0,5 et 1,5. According to an advantageous implementation method of the invention, an organic and / or mineral base is used. When using a mineral base, it is preferred to use it in a molar ratio of mineral base to the phenolic derivative of between 0.4 and 1 and when using a pyridine, it is preferred to use it in a molar ratio pyridine with phenolic derivative between 0.5 and 1.5.
La température de mise en oeuvre de la réaction est comprise de préférence entre -200C et 1150C et encore plus préférentiellement entre 0 et 9OcC. The reaction implementation temperature is preferably between -200C and 1150C and even more preferably between 0 and 9OcC.
Il est avantageux d'utiliser une pression comprise entre 1 et 10 bars. La pression sera simplement adaptée par l'homme de l'art aux réactifs mis en présence. It is advantageous to use a pressure between 1 and 10 bars. The pressure will simply be adapted by a person skilled in the art to the reactants brought into contact.
On opère de préférence en l'absence d'oxygène. The operation is preferably carried out in the absence of oxygen.
On peut citer parmi les produits obtenus par le procédé de la présente invention, les trifluorométhyldiphényléthers, les trifluorométhylphénols, les chlorotrifluorométhylphénols, les méthyltrifluorométhylphénols, les méthoxytrifluorométhylphénols, les aminotrifluorométhylphénols,... Among the products obtained by the process of the present invention, mention may be made of trifluoromethyldiphenyl ethers, trifluoromethylphenols, chlorotrifluoromethylphenols, methyltrifluoromethylphenols, methoxytrifluoromethylphenols, aminotrifluoromethylphenols, etc.
Les produits objets du procédé de l'invention sont notamment utilisés comme intermédiaires de synthèse dans l'industrie pharmaceutique ou phytosanitaire. The products which are the subject of the process of the invention are especially used as synthesis intermediates in the pharmaceutical or phytosanitary industry.
L'invention va être plus complètement décrite à l'aide des exemples suivants qui ne devront pas être considérés comme limitatifs de l'invention. The invention will be more fully described with the aid of the following examples which should not be considered as limiting the invention.
EXEMPLE 1
Dans un flacon en verre épais, on introduit 10 g de phénol, 25 ml de diméthylformamide, 10 ml de méthyl-2 pyridine, 1 g de zinc et 8 g de métabisulfite de sodium. On fait le vide dans le flacon.EXAMPLE 1
10 g of phenol, 25 ml of dimethylformamide, 10 ml of 2-methyl pyridine, 1 g of zinc and 8 g of sodium metabisulfite are introduced into a thick glass bottle. We empty the bottle.
Celui-ci est alors thermostaté à 600C. On introduit 8 g de dioxyde de soufre et le flacon est agité pendant 4 heures sous une pression de bromotrifluorométhane qui est maintenue entre 2,7 et 1,5 atmosphères. Le flacon est alors ouvert. On ajoute 50 g de glace, 15 ml d'acide chlorhydrique concentré. Le mélange est extrait à l'éther, la phase éthérée est rincée avec de l'acide chlorhydrique dilué et une solution de chlorure de sodium puis séchée avec du sulfate de magnésium.On obtient par distillation
1) 3,5 g de trifluorométhyl-2 phénol Eb 147-1480C
(rendement 20 %) #F = - 61,6 ppm #H = 7,48 ppm (2 H, d) 7 ppm (2 H, t)
Le résidu est purifié par chromatographie en phase gazeuse,
il contient, outre le phénol non réagi
2) 1,7 g de trifluorométhyl-4 phénol (rendement 10 %)
= - 60,3 ppm dH = 7,53 ppm (2 H, d)
6,93 ppm (2 H, d, J : 8,5 Hz)
EXEMPLE 2
On procède comme à l'exemple 1 en remplaçant le phénol par 10 g de chloro-3 phénol.This is then thermostatically controlled at 600C. 8 g of sulfur dioxide are introduced and the flask is shaken for 4 hours under a bromotrifluoromethane pressure which is maintained between 2.7 and 1.5 atmospheres. The bottle is then opened. 50 g of ice, 15 ml of concentrated hydrochloric acid are added. The mixture is extracted with ether, the ethereal phase is rinsed with dilute hydrochloric acid and a solution of sodium chloride and then dried with magnesium sulphate. This is obtained by distillation
1) 3.5 g of 2-trifluoromethyl phenol Eb 147-1480C
(yield 20%) #F = - 61.6 ppm #H = 7.48 ppm (2 H, d) 7 ppm (2 H, t)
The residue is purified by gas chromatography,
it contains, in addition to the unreacted phenol
2) 1.7 g of 4-trifluoromethyl phenol (10% yield)
= - 60.3 ppm dH = 7.53 ppm (2 H, d)
6.93 ppm (2 H, d, J: 8.5 Hz)
EXAMPLE 2
The procedure is as in Example 1, replacing the phenol with 10 g of 3-chloro-phenol.
Après 4 heures de réaction et extraction à l'éther, on obtient
1) 2,6 g de chloro-3 trifluorométhyl-2 phénol
Rdt : 17 % dF = - 55 ppm dH = 7,23 ppm (IH, t, J : 8,5 Hz)
6,93 ppm (2 H, m)
2) 2,9 g de chloro-5 trifluorométhyl-2 phénol
Rdt : 19 % # = - 60,3 ppm #H = 7,4 ppm (IH, d, J : 8,5 Hz)
6,93 ppm (2 H, m)
3) 1,8 g de chloro-3 trifluorométhyl-4 phénol
Rdt : 12 % FF = - 62 ppm dH = 7,53 ppm (IH, d, J : 8,5Hz)
6,87 ppm (2 H, m)
EXEMPLE 3
On procède comme à l'exemple 1 en remplaçant le phénol par 10 g de chloro-2 phénol.After 4 hours of reaction and extraction with ether, we obtain
1) 2.6 g of 3-chloro-2-trifluoromethyl phenol
Yid: 17% dF = - 55 ppm dH = 7.23 ppm (IH, t, J: 8.5 Hz)
6.93 ppm (2 H, m)
2) 2.9 g of 5-chloro-2-trifluoromethyl phenol
Yid: 19% # = - 60.3 ppm #H = 7.4 ppm (IH, d, J: 8.5 Hz)
6.93 ppm (2 H, m)
3) 1.8 g of 3-chloro-4-trifluoromethyl phenol
Yid: 12% FF = - 62 ppm dH = 7.53 ppm (IH, d, J: 8.5Hz)
6.87 ppm (2 H, m)
EXAMPLE 3
The procedure is as in Example 1, replacing the phenol with 10 g of 2-chloro-phenol.
Après 4 heures de réaction et extraction à l'éther, on obtient
1) 1,4 g de chloro-6 trifluorométhyl-2 phénol Rdt : 9 %
= = 7,37 ppm (2 H, d) 6,63 ppm (IH, t, J : 8,5 Hz)
= = - 62,6 ppm (s)
2) 0,9 g de chloro-2 trifluorométhyl-4 phénol Rdt : 6 % #H = 7,46 ppm (IH, d, J : 1 Hz)
7,27 ppm (IH, dxd, J = 8,5 Hz ; 1 Hz)
6,63 ppm (IH, d, J : 8,5 Hz) dF = - 61 ppm
EXEMPLE 4
On procède comme à l'exemple 1 en remplaçant le phénol par 10 g de méthyl-3 phénol.After 4 hours of reaction and extraction with ether, we obtain
1) 1.4 g of 6-chloro-2-trifluoromethyl phenol Yield: 9%
= = 7.37 ppm (2 H, d) 6.63 ppm (IH, t, J: 8.5 Hz)
= = - 62.6 ppm (s)
2) 0.9 g of 2-chloro-4-trifluoromethyl phenol Yield: 6% #H = 7.46 ppm (IH, d, J: 1 Hz)
7.27 ppm (IH, dxd, J = 8.5 Hz; 1 Hz)
6.63 ppm (IH, d, J: 8.5 Hz) dF = - 61 ppm
EXAMPLE 4
The procedure is as in Example 1, replacing the phenol with 10 g of 3-methylphenol.
Après 4 heures de réaction et extraction à l'éther, on obtient
1) 4,2 g de méthyl-3 trifluorométhyl-2 phénol Rdt 26 %
Eb 23 mm Hg 77-79 C dF = - 53,3 ppm (q) #H = 7,27 ppm (IH, dxd, J = 8 Hz, J = 9 Hz) ; 6,8 ppm (2 H, d)
2,43 ppm (3H, q, J HF = 3 Hz)
2) 2,6 g de méthyl-5 trifluorométhyl-2 phénol Rdt 16 %
Eb 23 mm Hg 84-860C #F = - 60 ppm dH = 7,4 ppm (IH, d, J : 8,5 Hz) 6,8 ppm (2H, d) 2,27 ppm
(3H, s)
On purifie par chromatographie en phase vapeur
3) 3,9 g de méthyl-3 trifluorométhyl-4 phénol Rdt 24 %
= - 59 ppm (s large) #H = 7,43 ppm (IH, d, J = 8,5 Hz)
6,7 ppm (2 H, m) 2,37 ppm (3H, s large)
EXEMPLE 5
On procède comme à l'exemple 1 en remplaçant le phénol par 10 g de méthoxy-3 phénol.After 4 hours of reaction and extraction with ether, we obtain
1) 4.2 g of 3-methyl-2-trifluoromethyl phenol Yield 26%
Eb 23 mm Hg 77-79 C dF = - 53.3 ppm (q) #H = 7.27 ppm (IH, dxd, J = 8 Hz, J = 9 Hz); 6.8 ppm (2 H, d)
2.43 ppm (3H, q, J HF = 3 Hz)
2) 2.6 g of 5-methyl-2-trifluoromethyl phenol Yield 16%
Eb 23 mm Hg 84-860C #F = - 60 ppm dH = 7.4 ppm (IH, d, J: 8.5 Hz) 6.8 ppm (2H, d) 2.27 ppm
(3H, s)
Purify by vapor phase chromatography
3) 3.9 g of 3-methyl-4-trifluoromethyl phenol Yield 24%
= - 59 ppm (s wide) #H = 7.43 ppm (IH, d, J = 8.5 Hz)
6.7 ppm (2H, m) 2.37 ppm (3H, wide s)
EXAMPLE 5
The procedure is as in Example 1, replacing the phenol with 10 g of 3-methoxyphenol.
Après 3 heures de réaction et extraction à éther, on obtient
1) 3,9 g de méthoxy-3 trifluorométhyl-2 phénol Rdt 25 Z
= - 53,8 ppm dH = 7,33 ppm (IH, t, J = 8,5 Hz)
6,56 ppm (2 H, d) 3,87 ppm (3 H, s)
2) 3,9 g de méthoxy-5 trifluorométhyl-2 phénol Rdt 25 % #F = - 59 ppm dH = 7,43 ppm (IH, d, J : 8,5 Hz)
6,53 ppm (2 H, m) 3,77 ppm (3 H, s)
3) 3,9 g de méthoxy-3 trifluorométhyl-4 phénol Rdt 25 z dF = - 61 ppm dH = 7,43 ppm (IH, d, J : 8,5 Hz)
6,36 ppm (1 H, m) 3,83 ppm (3 H, s)
EXEMPLE 6
On procède comme à l'exemple 1 en remplaçant le phénol par 10 g de diméthoxy 1,3 benzène.After 3 hours of reaction and extraction with ether, we obtain
1) 3.9 g of 3-methoxy-2-trifluoromethyl phenol Yield 25 Z
= - 53.8 ppm dH = 7.33 ppm (IH, t, J = 8.5 Hz)
6.56 ppm (2 H, d) 3.87 ppm (3 H, s)
2) 3.9 g of 5-methoxy-2-trifluoromethyl phenol Yield 25% #F = - 59 ppm dH = 7.43 ppm (IH, d, J: 8.5 Hz)
6.53 ppm (2 H, m) 3.77 ppm (3 H, s)
3) 3.9 g of 3-methoxy-4-trifluoromethyl phenol Yield 25 z dF = - 61 ppm dH = 7.43 ppm (IH, d, J: 8.5 Hz)
6.36 ppm (1 H, m) 3.83 ppm (3 H, s)
EXAMPLE 6
The procedure is as in Example 1, replacing the phenol with 10 g of 1,3-benzene dimethoxy.
Après 4 heures de réaction et extraction à l'éther, on obtient
1) 3,3 g de diméthoxy-2,4 trifluorométhylbenzène Rdt 23 % dH = 7,4 ppm (IH, d, J : 8,5Hz) 6,8 ppm (IH, s large)
6,45 ppm (1H, m) 3,83 ppm (3 H, s) 3,78 ppm (3 H, s) dF = - 61,3 ppm (s)
2) 0,7 g de diméthoxy-2,6 trifluorométhylbenzène Rdt 4 %
= = 7,45 ppm (IH, t) 6,63 ppm (2 H, d, J : 8,5 Hz)
3,88 ppm (6 H, s) dF = T 54 ppm (s)
EXEMPLE 7
Dans un flacon en verre épais, on introduit 10 g de dihydroxy-1,3 benzène, 25 ml de diméthylformamide, 1 g de zinc et 10 ml de méthyl-2 pyridine.After 4 hours of reaction and extraction with ether, we obtain
1) 3.3 g of 2,4-dimethoxy-trifluoromethylbenzene Yield 23% dH = 7.4 ppm (IH, d, J: 8.5 Hz) 6.8 ppm (IH, s broad)
6.45 ppm (1H, m) 3.83 ppm (3H, s) 3.78 ppm (3H, s) dF = - 61.3 ppm (s)
2) 0.7 g of 2,6-dimethoxy trifluoromethylbenzene Yield 4%
= = 7.45 ppm (IH, t) 6.63 ppm (2 H, d, J: 8.5 Hz)
3.88 ppm (6 H, s) dF = T 54 ppm (s)
EXAMPLE 7
10 g of 1,3-dihydroxy benzene, 25 ml of dimethylformamide, 1 g of zinc and 10 ml of 2-methyl pyridine are introduced into a thick glass bottle.
Le flacon est placé dans un appareil de Parr. The bottle is placed in a Parr device.
On fait le vide dans le flacon ; on introduit 8 g de dioxyde de soufre. Le flacon est agité pendant 3 heures sous une pression de bromotrifluorométhane qui est maintenue entre 2,7 et 1?4 atmosphères. La réaction est exothermique. Le flacon est ensuite ouvert, on ajoute 50 g de glace, 15 ml d'acide chlorhydrique concentré. Le mélange est extrait à l'éther. On obtient un mélange de
1) 1 g de dihydroxy-1,3 trifluorométhyl-2 benzène Rdt 6 Z
F = - 53,3 ppm
2) 2,8 g de dihydroxy-1,3 trifluorométhyl-4 benzène Rdt 17 Z
dF = ~ 58,8 ppm
EXEMPLE 8
On procède comme à l'exemple 7 en remplaçant le dihydroxybenzène par 10 g (0,02 mole) d'amino-3 phénol.We empty the bottle; 8 g of sulfur dioxide are introduced. The flask is shaken for 3 hours under a bromotrifluoromethane pressure which is maintained between 2.7 and 1? 4 atmospheres. The reaction is exothermic. The bottle is then opened, 50 g of ice, 15 ml of concentrated hydrochloric acid are added. The mixture is extracted with ether. We get a mixture of
1) 1 g of 1,3-dihydroxy-2-trifluoromethyl benzene Yield 6 Z
F = - 53.3 ppm
2) 2.8 g of 1,3-dihydroxy-4-trifluoromethyl benzene Yield 17 Z
dF = ~ 58.8 ppm
EXAMPLE 8
The procedure is as in Example 7, replacing the dihydroxybenzene with 10 g (0.02 mole) of 3-amino phenol.
Après 3 heures de réaction et extraction à l'éther, on obtient un mélange qui est purifié par chromatographie sur plaque de -silice avec comme éluant un mélange benzène-acétate d'éthyle 90/10
1) 0,5 g de ditrifluorométhyl amino-3 phénol Rdt 3 Z
2) 2,8 g d'amino-3 trifluorométhyl-2 phénol
Rdt 17 2 dF = - 54,5 ppm PF 1210C
3) 2,8 g d'amino-3 trifluorométhyl-4 phénol
Rdt 17 % dF = - 61 ppm PF lOl0C
4) 2,8 g d'amino-5 trifluorométhyl-2 phénol
Rdt 17 % #F = - 60,6 ppm PF 131 C
EXEMPLE 9
On procède comme à l'exemple 8 en remplaçant l'amino-3 phénol par 10 g d'amino-2 phénol.After 3 hours of reaction and extraction with ether, a mixture is obtained which is purified by chromatography on a silica plate with as eluent a benzene-ethyl acetate mixture 90/10
1) 0.5 g of ditrifluoromethyl-3-amino phenol Yd 3 Z
2) 2.8 g of 3-amino-2-trifluoromethylphenol
Yield 17 2 dF = - 54.5 ppm PF 1210C
3) 2.8 g of 3-amino-4-trifluoromethyl phenol
Yield 17% dF = - 61 ppm PF lOl0C
4) 2.8 g of 5-amino-2-trifluoromethylphenol
Yield 17% #F = - 60.6 ppm PF 131 C
EXAMPLE 9
The procedure is as in Example 8, replacing 3-amino phenol with 10 g of 2-amino phenol.
Après 3 heures de réaction et extraction à l'éther, on obtient
1) 2 g d'amino-2 ditrifluorométhylphénol (rendement 9 Z)
2) 3,1 g d'amino-2 trifluorométhyl-3 phénol (rendement 19 %)
F = - 62 ppm
3) 4,8 g d'amino-2 trifluorométhyl-5 phénol (rendement 30 %)
F = - 59,4 ppm
EXEMPLE 10
On procède comme à l'exemple 1 en remplaçant le bromotrifluorométhane par 40 g d'iodopentafluoroéthane et en thermostatant le flacon à 200C.After 3 hours of reaction and extraction with ether, we obtain
1) 2 g of amino-2 ditrifluoromethylphenol (yield 9 Z)
2) 3.1 g of 2-amino-3-trifluoromethyl phenol (yield 19%)
F = - 62 ppm
3) 4.8 g of 2-amino-5-trifluoromethyl phenol (yield 30%)
F = - 59.4 ppm
EXAMPLE 10
The procedure is as in Example 1, replacing the bromotrifluoromethane with 40 g of iodopentafluoroethane and thermostating the flask at 200C.
Après 3 heures de réaction et extraction à l'éther, on obtient
1) 1,35 g de pentafluoroéthyl-2 phénol Rdt 6 % dF - ~ 83,7 ppm (3F) - 111,7 ppm (2F)
2) 1,6 g de pentafluoroéthyl-4 phénol
Rdt 7 X dF - 84,3 ppm (3F) - 113,3 ppm (2F)
EXEMPLE 11
Dans un erlenmeyer, on introduit 2 g de phénol, 5 ml de diméthylformamide, 2 ml de méthyl-2 pyridine, 0,2 g de zinc, 1 g de métabisulfite de sodium.After 3 hours of reaction and extraction with ether, we obtain
1) 1.35 g of 2-pentafluoroethylphenol Yield 6% dF - ~ 83.7 ppm (3F) - 111.7 ppm (2F)
2) 1.6 g of 4-pentafluoroethylphenol
Yield 7 X dF - 84.3 ppm (3F) - 113.3 ppm (2F)
EXAMPLE 11
2 g of phenol, 5 ml of dimethylformamide, 2 ml of 2-methyl pyridine, 0.2 g of zinc, 1 g of sodium metabisulfite are introduced into an Erlenmeyer flask.
L'atmosphère dans l'erlenmeyer est constituée par un mélange argon/dioxyde de soufre 50/50. The atmosphere in the Erlenmeyer flask is made up of a 50/50 argon / sulfur dioxide mixture.
On ajoute sous agitation 9 g d'iodure de perfluorohexyle. On ajoute ensuite 10 g de glace, 5 ml d'acide chlorhydrique concentré. 9 g of perfluorohexyl iodide are added with stirring. Then added 10 g of ice, 5 ml of concentrated hydrochloric acid.
Le mélange est extrait à l'éther ; on obtient après purification :
1) 1,2 g de perfluorohexyl-2 phénol Rdt 14 Z #F = - 80 ppm (3F) - 107 ppm (2F) - 121 ppm (6F)
- 125 ppm (2F) dH = 7,36 ppm (2H, d) 7 ppm (2H, t, J : 8,5 Hz)
2) 1,2 g de perfluorohexyl-4 phénol Rdt 14 Z
dF - 80 ppm (3F) - 108 ppm (2F) - 121 ppm (6F)
- 125 ppm (2F)
7,43 ppm (2H, d) 7,03 (2H, d) J : 8,5 Hz The mixture is extracted with ether; after purification,
1) 1.2 g of 2-perfluorohexylphenol Yield 14 Z #F = - 80 ppm (3F) - 107 ppm (2F) - 121 ppm (6F)
- 125 ppm (2F) dH = 7.36 ppm (2H, d) 7 ppm (2H, t, J: 8.5 Hz)
2) 1.2 g of 4-perfluorohexylphenol Yield 14 Z
dF - 80 ppm (3F) - 108 ppm (2F) - 121 ppm (6F)
- 125 ppm (2F)
7.43 ppm (2H, d) 7.03 (2H, d) J: 8.5 Hz
Claims (16)
Priority Applications (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR8515857A FR2589147B1 (en) | 1985-10-25 | 1985-10-25 | PROCESS FOR THE PREPARATION OF PERFLUOROALKYL PHENOLIC DERIVATIVES |
| EP86420130A EP0206951B1 (en) | 1985-05-22 | 1986-05-16 | Process for the perfluoroalkylation of aromatic derivatives |
| DE8686420130T DE3669709D1 (en) | 1985-05-22 | 1986-05-16 | METHOD FOR PERFLUORALCYLATING AROMATIC DERIVATIVES. |
| AT86420130T ATE51218T1 (en) | 1985-05-22 | 1986-05-16 | PROCESS FOR THE PERFLUORO ALKYLATION OF AROMATIC DERIVATIVES. |
| CA000509651A CA1252792A (en) | 1985-05-22 | 1986-05-21 | Aromatic derivatives perfluoroalkylation process |
| US06/865,346 US4731450A (en) | 1985-05-22 | 1986-05-21 | Process for perfluoroalkylation of aromatic derivatives |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR8515857A FR2589147B1 (en) | 1985-10-25 | 1985-10-25 | PROCESS FOR THE PREPARATION OF PERFLUOROALKYL PHENOLIC DERIVATIVES |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| FR2589147A1 true FR2589147A1 (en) | 1987-04-30 |
| FR2589147B1 FR2589147B1 (en) | 1987-11-20 |
Family
ID=9324191
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| FR8515857A Expired FR2589147B1 (en) | 1985-05-22 | 1985-10-25 | PROCESS FOR THE PREPARATION OF PERFLUOROALKYL PHENOLIC DERIVATIVES |
Country Status (1)
| Country | Link |
|---|---|
| FR (1) | FR2589147B1 (en) |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2307785A1 (en) * | 1971-08-25 | 1976-11-12 | Dow Chemical Co | AROMATIC COMPOUNDS CHLORINATION PROCESS |
-
1985
- 1985-10-25 FR FR8515857A patent/FR2589147B1/en not_active Expired
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2307785A1 (en) * | 1971-08-25 | 1976-11-12 | Dow Chemical Co | AROMATIC COMPOUNDS CHLORINATION PROCESS |
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| FR2589147B1 (en) | 1987-11-20 |
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