WO1997021656A1 - Method for making fluoroalkanols - Google Patents

Method for making fluoroalkanols Download PDF

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Publication number
WO1997021656A1
WO1997021656A1 PCT/FR1996/001971 FR9601971W WO9721656A1 WO 1997021656 A1 WO1997021656 A1 WO 1997021656A1 FR 9601971 W FR9601971 W FR 9601971W WO 9721656 A1 WO9721656 A1 WO 9721656A1
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compound
formula
iii
salt
reaction
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PCT/FR1996/001971
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French (fr)
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Jean-Philippe Gillet
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Elf Atochem S.A.
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Priority to AU11017/97A priority Critical patent/AU1101797A/en
Publication of WO1997021656A1 publication Critical patent/WO1997021656A1/en

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/09—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis
    • C07C29/12—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis of esters of mineral acids
    • C07C29/124—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis of esters of mineral acids of halides
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/09—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis
    • C07C29/095—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis of esters of organic acids

Definitions

  • the present invention relates to a process for the manufacture of fluoroalkanols of formula:
  • the main access routes to 2,2,2-trifluoroethanol are, on the one hand, the hydrogenation reactions of trifluoroacetic acid and its. derivatives, such as trifluoroacetic anhydride, trifluoroacetyl chloride, fluorine or fluorine hydrate, hemiacetal of fluorine, and methyl or ethyl or trifluoroethyl trifluoroacetate, and, on the other hand, hydrolysis direct, or via the formation of an acetate, 2-chloro-1,1,1-trifluoroethane.
  • trifluoroacetic acid and its. derivatives such as trifluoroacetic anhydride, trifluoroacetyl chloride, fluorine or fluorine hydrate, hemiacetal of fluorine, and methyl or ethyl or trifluoroethyl trifluoroacetate
  • R representing an alkyl or hydroxyalkyl group having not more than 19 carbon atoms and R '"representing a hydroxyalkyl group having not more than 5 carbon atoms
  • ⁇ -hydroxybutyrates of K or Na are cited as usable carboxylic acid salts.
  • the present invention therefore has for its object a process for the manufacture of a compound of formula (I) as defined above, characterized in that it is reacted under a pressure of between 0.10 and 2 bar, a a temperature of 100 ° C 280 ° C, in a polar aprotic solvent, a compound of formula (II):
  • X represents a halogen
  • - Rf is as defined above, with a salt of formula (III):
  • the reaction is generally carried out at normal atmospheric pressure or close to normal, and at a temperature between 120 "C and 240 ° C.
  • a potassium salt is preferably used as the salt of formula (III).
  • the polar aprotic solvent is chosen for example from sulfolane (tetramethylene sulfone), N, N-dimethylformamide, dimethylsulfoxide, N, N-dimethylacetamide, N-methylpyrrolidone, 1, 3-dimethyl-2-imidazolidinone, 1, 3-dimethyl-3, 4, 5, 6-tetrahydro-2-pyrimidinone and their mixtures.
  • sulfolane or 1, 3-dimethyl-2-imidazolidinone is used.
  • reaction is advantageously carried out with a molar ratio of the compound of formula (II) to the salt of formula (III) of between approximately 0.5 and 10, preferably between approximately 1 and 7.
  • operation is generally carried out at a concentration of the salt of formula (III) of between 5 and 40% by weight, preferably between 10 and 25% by weight relative to the polar aprotic solvent.
  • the salt of formula (III) previously prepared is used in the reaction.
  • a polar aprotic solvent and the salt (III) are charged to the reactor.
  • the medium is brought to the reaction temperature with stirring, then the compound (II) is injected there.
  • the alcohol (I) forms distills as it goes and it is recover.
  • the reaction medium is cooled, and the salt MX is filtered.
  • the salt of formula (III) is formed in situ by engaging in the reaction a compound of formula (IV):
  • Y-butyrolactone or v-butyrolactam 6-valerolactone or ⁇ -valerolactam; 4-ethylbutyrolactone or 4-ethylbutyrolactam; and phthalide.
  • the pure alcohol (I) is obtained by distillation of the crude distillate.
  • the reaction medium is recycled in the same reaction by adding a base capable of forming it in situ composes it (III).
  • Forane 133a 2-chloro-1,1,1-trifluoroethane (CF 3 CH 2 C1)
  • DMI 1,3-dimethyl-2-imidazolidinone
  • the reactor used is a 500 cm glass reactor, provided with efficient stirring of the turbine type, a gas introduction pipe, and a rectification column.
  • Example 1 Manufacture of 2, 2, 2-trifluoroethanol by reaction of potassium 6-hydroxyhexanoate with Forane 133a
  • the trifluoroethanol forms distilled as it goes along and is condensed in a Dean-Stark.
  • the excess Forane 133a is recovered in a trap cooled by dry ice.
  • the reaction medium is cooled and the KC1 formed is filtered.
  • the trifluoroethanol formed distills as the reaction progresses. After 4 hours, the yield of trifluoroethanol relative to the potassium introduced is 85%.
  • Example 2 The procedure is as in Example 1, except that at the end of the reaction, the reaction medium is filtered to recover the KC1 generated by the reaction. The filtrate thus obtained is reengaged without treatment for another test. An aqueous solution of KOH (0.2 mole of KOH for 11.7 g of water) is added at room temperature, then the procedure is as in Example 2. The same reaction medium was thus used for five consecutive tests A â E.

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  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

A method for making a compound of formula (I) Rf - CH2 - OH, wherein a compound of formula (II) Rf - CH2 - X is reacted with a salt of formula (III) under a pressure of 0.10-2 bar and at a temperature of 100-280 °C in a polar aprotic solvent, the compound of formula (II) being fed continuously into a reactor into which compound (III) and the polar aprotic solvent have previously been fed, and the distilled compound (III) being continuously recovered as it is formed. In formulae (I), (II) and (III), Rf is C1-10 perfluorinated alkyl; X is halogen; each of R?1 and R2¿ is independently a hydrogen atom or a straight or branched C¿1-4? alkyl group, wherein two carbon atoms adjacent to the concatenation -(CR?1R2)¿m, taken together with the radicals to which they are attached, form part of an aliphatic or aromatic ring; m is 3, 4 or 5; A is O or NH; and M is an alkali metal.

Description

PROCEDE DE FABRICATION DE FLUOROALCANOLSPROCESS FOR THE MANUFACTURE OF FLUOROALCANOLS
La présente invention porte sur un procède de fabrication de fluoroalcanols de formule :The present invention relates to a process for the manufacture of fluoroalkanols of formula:
Rf - CH2 - OH (I) dans laquelle Rf représente un radical alkyle perfluoré en cl-c10' et en particulier du 2 ,2, 2-trifluoroéthanol .R f - CH 2 - OH (I) in which R f represents a perfluorinated alkyl radical in c l -c 10 ' and in particular of 2, 2, 2-trifluoroethanol.
Les principales voies d'accès au 2,2,2- trifluoroéthanol sont, d'une part, les reactions d'hydrogénation de l'acide trifluoroacétique et de ses . dérives, tels que l'anhydride trifluoroacétique, le chlorure de trifluoroacetyle, le fluoral ou hydrate de fluoral, l'hemiacetal du fluoral, et le trifluoroacétate de méthyle ou d'ethyle ou de trifluoroéthyle, et, d'autre part, l'hydrolyse directe, ou via la formation d'un acétate, du 2-chloro-l, 1, l-trifluoroethane.The main access routes to 2,2,2-trifluoroethanol are, on the one hand, the hydrogenation reactions of trifluoroacetic acid and its. derivatives, such as trifluoroacetic anhydride, trifluoroacetyl chloride, fluorine or fluorine hydrate, hemiacetal of fluorine, and methyl or ethyl or trifluoroethyl trifluoroacetate, and, on the other hand, hydrolysis direct, or via the formation of an acetate, 2-chloro-1,1,1-trifluoroethane.
L'hydrogénation de l'acide trifluoroacétique ou de ses dérives conduit a de très bons rendements, mais nécessite des conditions particulièrement dures (de pression et température élevées) , ainsi que l'emploi de catalyseurs a base de métaux précieux, dont le recyclage parait difficile.The hydrogenation of trifluoroacetic acid or its derivatives leads to very good yields, but requires particularly harsh conditions (high pressure and temperature), as well as the use of catalysts based on precious metals, the recycling of which appears to be difficult.
L'hydrolyse directe du 2-chloro-l, 1, 1- trifluoroethane en phase gazeuse, telle que décrite dans le brevet français n° 2 635 101, effectuée dans des conditions très dures (température de 490°C) en présence de LaPO^ comme catalyseur, conduit a des résultats très moyens (conversion : 19 % ; sélectivité : 62 %) .Direct hydrolysis of 2-chloro-1,1,1-trifluoroethane in the gas phase, as described in French Patent No. 2,635,101, carried out under very harsh conditions (temperature of 490 ° C) in the presence of LaPO ^ as a catalyst, leads to very average results (conversion: 19%; selectivity: 62%).
L'hydrolyse ou saponification en phase liquide de l'acétate de 2,2, 2-trifluoroéthyle, telle qu'illustrée dans les équations suivantes :The hydrolysis or saponification in the liquid phase of 2,2,2-trifluoroethyl acetate, as illustrated in the following equations:
CF3CH2C1 + CH3C02M > MCI + CH3CO2CH2CF3CF 3 CH 2 C1 + CH 3 C0 2 M> MCI + CH3CO2CH2CF3
CH3CO2CH2CF3 -f H20 ou KOH > CF3CH2OH + CH3COOH ou CH3COOKCH3CO 2 CH2CF3 -f H 2 0 or KOH> CF 3 CH 2 OH + CH3COOH or CH 3 COOK
peut être effectuée soit en une seule étape sans séparation de l'acétate intermédiaire, soit en deux étapes. Elle conduit généralement a d'assez bons résultats, mais elle s'effectue toujours sous pression, comme c'est le cas par exemple du procédé en milieu solvant aprotique polaire décrit dans la demande de brevet européen EP-A-101 526. Dans la demande de brevet britannique GB-A-can be carried out either in a single step without separation of the intermediate acetate, or in two steps. She generally leads to fairly good results, but it is always carried out under pressure, as is the case for example of the process in a polar aprotic solvent medium described in European patent application EP-A-101,526. In the application British patent GB-A-
2 117 376, il est proposé de conduire l'une des réactions suivantes, sous pression et dans la γ-butyrolactone comme solvant :2,117,376, it is proposed to carry out one of the following reactions, under pressure and in γ-butyrolactone as solvent:
H20 + RCOOM + CF3CH2Hal — > RCOOH + CF3CH2OH + MHal R"'COOM + CF3CH2Hal —s» CF3CH2OH + lactone + MHalH20 + RCOOM + CF 3 CH 2 Hal -> RCOOH + CF 3 CH 2 OH + MHal R "'COOM + CF 3 CH 2 Hal —s» CF 3 CH 2 OH + lactone + MHal
avec R représentant un groupe alkyle ou hydroxyalkyle n'ayant pas plus de 19 atomes de carbone et R'" représentant un groupe hydroxyalkyle n'ayant pas plus de 5 atomes de carbone (Cf. GB-A-2 117 376, page 1, lignes 37 et 55) . On cite les γ-hydroxybutyrates de K ou Na comme sels d'acides carboxyliques utilisables.with R representing an alkyl or hydroxyalkyl group having not more than 19 carbon atoms and R '"representing a hydroxyalkyl group having not more than 5 carbon atoms (Cf. GB-A-2 117 376, page 1, lines 37 and 55) The γ-hydroxybutyrates of K or Na are cited as usable carboxylic acid salts.
La demande de brevet français n' 94-07454 du 17 juin 1994 au nom de la Société déposante décrit un procède de préparation d'halogenoalcanolε en deux étapes : on fait d'abord reagir a la pression atmosphérique normale, dans un solvant aprotique polaire, un sel d'acide mono- ou dicarboxylique avec un compose perhalogéné R - CH2 - X (avec R = alkyle perhalogéné et X = halogène) , puis on saponifie l'ester ou le diester obtenu. II a maintenant ete découvert qu'il était possible de fabriquer directement un fluoroalcanol de formule (I) , a la pression atmosphérique normale, ou au voisinage de la pression atmosphérique normale, et en semi-continu, par simple barbotage d'un compose perfluoré Rf - CH2 - X dans un mélange d'un sel d'hydroxyacide ou d'aminoacide et d'un solvant aprotique polaire.French patent application No. 94-07454 of June 17, 1994 in the name of the applicant company describes a process for the preparation of haloalkanolol in two stages: first reacting at normal atmospheric pressure in a polar aprotic solvent, a salt of mono- or dicarboxylic acid with a perhalogenated compound R - CH 2 - X (with R = perhalogenated alkyl and X = halogen), then the ester or diester obtained is saponified. It has now been discovered that it is possible to directly manufacture a fluoroalkanol of formula (I), at normal atmospheric pressure, or in the vicinity of normal atmospheric pressure, and semi-continuously, by simple bubbling of a perfluorinated compound R f - CH 2 - X in a mixture of a hydroxy acid or amino acid salt and a polar aprotic solvent.
Les avantages résident dans le fait qu'il n'est pas nécessaire de disposer d'un matériel résistant a la pression, que l'on peut opérer en toute sécurité, que le produit final peut être récupère en continu par distillation au fur et a mesure de sa formation, que le milieu réactionnel peut être recycle par ajout d'une base, et, par rapport au procède selon la demande n' 94-07454 précitée, il n'y a plus de recyclage de sel d'acide anhydre a l'état solide. La présente invention a donc pour obiet un procède de fabrication d'un compose de formule (I) tel que défini ci-dessus, caractérise par le fait que l'on fait reagir sous une pression comprise entre 0,10 et 2 bar, a une température de 100*C a 280'C, dans un solvant aprotique polaire, un compose de formule (II) :The advantages lie in the fact that it is not necessary to have a pressure-resistant material, that it can be operated in complete safety, that the final product can be continuously recovered by distillation as and when measurement of its formation, that the reaction medium can be recycled by adding a base, and, with respect to the process according to the above-mentioned application No. 94-07454, there is no longer any recycling of anhydrous acid salt a solid state. The present invention therefore has for its object a process for the manufacture of a compound of formula (I) as defined above, characterized in that it is reacted under a pressure of between 0.10 and 2 bar, a a temperature of 100 ° C 280 ° C, in a polar aprotic solvent, a compound of formula (II):
Rf - CH2 - X (II) dans laquelle :R f - CH 2 - X (II) in which:
X représente un halogène ; et - Rf est tel que défini ci-dessus, avec un sel de formule (III) :X represents a halogen; and - Rf is as defined above, with a salt of formula (III):
Figure imgf000005_0001
Figure imgf000005_0001
dans laquelle :in which :
R et R^ représentent chacun indépendamment un atome d'hydrogène ou un groupe alkyle linéaire ou ramifie en C1-C4, deux atomes de carbone voisins de l'enchaînement -(CR R )m pouvant avec les radicaux qu'ils portent faire partie d'un cycle aliphatique ou aromatique ; m = 3 , 4 ou 5 ; A représente 0 ou NH ; et M représente un métal alcalin, le compose de formule (II) étant introduit en continu dans le reacteur dans lequel on a préalablement introduit le compose (III) et le solvant aprotique polaire, et le compose (I) qui distille étant récupère en continu au fur et a mesure de sa formation.R and R ^ each independently represent a hydrogen atom or a linear or branched C1-C 4 alkyl group, two carbon atoms neighboring the chain - (CR R) m may, together with the radicals which they carry an aliphatic or aromatic cycle; m = 3, 4 or 5; A represents 0 or NH; and M represents an alkali metal, the compound of formula (II) being introduced continuously into the reactor into which the compound (III) and the polar aprotic solvent have previously been introduced, and the compound (I) which distills being continuously recovered as it is formed.
La reaction est généralement conduite a la pression atmosphérique normale ou proche de la normale, et a une température comprise entre 120"C et 240'C.The reaction is generally carried out at normal atmospheric pressure or close to normal, and at a temperature between 120 "C and 240 ° C.
Comme composé de formule (II) , on peut utiliser le 2-chloro-l, 1, 1-trifluoroethane, le 2-bromo-l, 1, 1- trifluoroethane et le 2-iodo-l, 1, 1-trifluoroethane.As the compound of formula (II), 2-chloro-1,1,1-trifluoroethane, 2-bromo-1,1,1-trifluoroethane and 2-iodo-1,1,1-trifluoroethane can be used.
Comme sel de formule (III), on utilise, de préférence, un sel de potassium.As the salt of formula (III), a potassium salt is preferably used.
A titre d'exemples des composes de formule (III) , on peut citer les sels de métaux alcalins de 1 acide 6- hydroxy (ou 6-amino) hexanoique ; de l'acide 4-hydroxy (ou 4-amino) butyrique ; de l'acide 5-hydroxy (ou 5-amιno) pentanoïque ; de l'acide 4-hydroxy (ou 4-amino) 4-ethyl butyrique ; et de l'acide 2-hydroxyméthyl benzoïque.As examples of the compounds of formula (III), mention may be made of the alkali metal salts of 1 6-hydroxy (or 6-amino) hexanoic acid; 4-hydroxy (or 4-amino) butyric acid; 5-hydroxy (or 5-amιno) pentanoic acid; 4-hydroxy (or 4-amino) 4-ethyl butyric acid; and 2-hydroxymethyl benzoic acid.
On choisit le solvant aprotique polaire par exemple parmi le sulfolane (tétramethylene suifone) , le N,N- diméthylformamide, le dimethylsulfoxyde, le N,N- dimethylacetamide, la N-méthylpyrrolidone, la 1, 3-dimethyl- 2-imidazolidinone, la 1, 3-dimethyl-3 , 4 ,5, 6-tetrahydro-2- pyrimidinone et leurs mélanges. De préférence, on utilise le sulfolane ou la 1, 3-dimethyl-2-imidazolidinone.The polar aprotic solvent is chosen for example from sulfolane (tetramethylene sulfone), N, N-dimethylformamide, dimethylsulfoxide, N, N-dimethylacetamide, N-methylpyrrolidone, 1, 3-dimethyl-2-imidazolidinone, 1, 3-dimethyl-3, 4, 5, 6-tetrahydro-2-pyrimidinone and their mixtures. Preferably, sulfolane or 1, 3-dimethyl-2-imidazolidinone is used.
Par ailleurs, on conduit avantageusement la reaction avec un rapport molaire du compose de formule (II) au sel de formule (III) compris entre environ 0,5 et 10, de préférence entre environ 1 et 7. En outre, on opère généralement a une concentration du sel de formule (III) comprise entre 5 et 40% en poids, de préférence entre 10 et 25% en poids par rapport au solvant aprotique polaire.Furthermore, the reaction is advantageously carried out with a molar ratio of the compound of formula (II) to the salt of formula (III) of between approximately 0.5 and 10, preferably between approximately 1 and 7. In addition, the operation is generally carried out at a concentration of the salt of formula (III) of between 5 and 40% by weight, preferably between 10 and 25% by weight relative to the polar aprotic solvent.
Conformément a un premier mode de réalisation du procède de l'invention, on engage dans la reaction le sel de formule (III) préalablement prépare. Dans ce cas, on charge, dans le réacteur, un solvant aprotique polaire et le sel (III) . On porte le milieu à la température de reaction sous agitation, puis on y injecte le compose (II) . L'alcool (I) forme distille au fur et a mesure et il est récupère. Le milieu réactionnel est refroidi, et on filtre le sel MX forme.In accordance with a first embodiment of the process of the invention, the salt of formula (III) previously prepared is used in the reaction. In this case, a polar aprotic solvent and the salt (III) are charged to the reactor. The medium is brought to the reaction temperature with stirring, then the compound (II) is injected there. The alcohol (I) forms distills as it goes and it is recover. The reaction medium is cooled, and the salt MX is filtered.
Conformément a un second mode de réalisation du procédé de l'invention, on forme le sel de formule (III) in situ en engageant dans la réaction un compose de formule (IV) :In accordance with a second embodiment of the process of the invention, the salt of formula (III) is formed in situ by engaging in the reaction a compound of formula (IV):
Figure imgf000007_0001
Figure imgf000007_0001
dans laquelle A, R1 et R2 sont tels que définis ci-dessus et une base telle que KOH, K2C03. Dans ce cas, on introduit, dans le reacteur, le solvant aprotique polaire, le compose (IV) et une solution basique. On porte le milieu a la température de reaction sous agitation. Durant la montée en température, la majeure partie de l'eau introduite distille. Puis, on injecte le compose (II) . La suite de la reaction s'opère comme dans le premier mode de réalisation.in which A, R 1 and R 2 are as defined above and a base such as KOH, K 2 C0 3 . In this case, the polar aprotic solvent, the compound (IV) and a basic solution are introduced into the reactor. The medium is brought to the reaction temperature with stirring. During the rise in temperature, most of the water introduced distills. Then, we inject the compound (II). The rest of the reaction takes place as in the first embodiment.
Des composés de formule (IV) que l'on peut mettre en oeuvre sont l'e-caprolactone ou l'e-caprolactame ; laCompounds of formula (IV) which can be used are e-caprolactone or e-caprolactam; the
Y-butyrolactone ou le v-butyrolactame ; la 6-valerolactone ou le δ-valerolactame ; la 4-ethylbutyrolactone ou le 4-ethylbutyrolactame ; et le phtalide.Y-butyrolactone or v-butyrolactam; 6-valerolactone or δ-valerolactam; 4-ethylbutyrolactone or 4-ethylbutyrolactam; and phthalide.
L'alcool (I) pur est obtenu par distillation du distillât brut.The pure alcohol (I) is obtained by distillation of the crude distillate.
Conformément à une autre caractéristique particulière du procédé selon l'invention, après avoir récupère le compose (I) et retiré du milieu réactionnel le sel formé MX, on recycle le milieu réactionnel dans la même réaction en y ajoutant une base capable de former in situ le compose (III) .In accordance with another particular characteristic of the process according to the invention, after recovering the compound (I) and removing from the reaction medium the salt formed MX, the reaction medium is recycled in the same reaction by adding a base capable of forming it in situ composes it (III).
Pour mieux illustrer l'objet de la présente invention, on va en décrire ci-apres, a titre indicatif et non limitatif, plusieurs exemples de réalisation. Les abréviations utilisées sont les suivantes :To better illustrate the object of the present invention, we will describe below, for information and non-limiting, several exemplary embodiments. The abbreviations used are as follows:
Forane 133a : 2-chloro-l, 1, 1-trifluoroethane (CF3CH2C1) DMI : 1, 3-diméthyl-2-imidazolidinoneForane 133a: 2-chloro-1,1,1-trifluoroethane (CF 3 CH 2 C1) DMI: 1,3-dimethyl-2-imidazolidinone
Dans tous les exemples, le réacteur utilisé est un reacteur en verre de 500 cm , muni d'une agitation efficace de type turbine, d'une canne d'introduction de gaz, et d'une colonne de rectification.In all the examples, the reactor used is a 500 cm glass reactor, provided with efficient stirring of the turbine type, a gas introduction pipe, and a rectification column.
Exemple 1 : Fabrication du 2 ,2 ,2-trifluoroéthanol par réaction du 6-hydroxyhexanoate de potassium avec le Forane 133aExample 1: Manufacture of 2, 2, 2-trifluoroethanol by reaction of potassium 6-hydroxyhexanoate with Forane 133a
Dans le réacteur, on charge 34 g (0,2 mole) de 6- hydroxyhexanoate de potassium dans 289 g de DMI. Le milieu réactionnel est porté à 210'C sous bonne agitation. Puis on introduit en continu le Forane 133a à un débit moyen de 40 g/h, à pression atmosphérique, pendant 4 h.34 g (0.2 mole) of potassium 6-hydroxyhexanoate are charged to 289 g of DMI in the reactor. The reaction medium is brought to 210 ° C. with good stirring. Then the Forane 133a is introduced continuously at an average flow rate of 40 g / h, at atmospheric pressure, for 4 h.
Le trifluoroéthanol forme distille au fur et a mesure et est condensé dans un Dean-Stark. Le Forane 133a excédentaire est récupéré dans un piège refroidi par de la carboglace. Le milieu réactionnel est refroidi et on filtre le KC1 formé.The trifluoroethanol forms distilled as it goes along and is condensed in a Dean-Stark. The excess Forane 133a is recovered in a trap cooled by dry ice. The reaction medium is cooled and the KC1 formed is filtered.
La conversion du 6-hydroxyhexanoate de potassium est de 100%, et on obtient un rendement de 81% en trifluoroéthanol par rapport à ce même sel.The conversion of potassium 6-hydroxyhexanoate is 100%, and a yield of 81% is obtained in trifluoroethanol relative to this same salt.
Exemple 2 : Fabrication du 2 ,2 ,2-trifluoroéthanol par réaction avec le Forane 133a du 6-hydroxy- hexanoate de potassium préparé in situExample 2 Production of 2,2,2-trifluoroethanol by reaction with Forane 133a of potassium 6-hydroxyhexanoate prepared in situ
Dans le réacteur, on charge 22,8 g (0,2 mole) d'ε-caprolactone dans 289 g de DMI. Puis on coule a la température ambiante 22,8 g d'une solution aqueuse de KOH a 49%. Le milieu réactionnel est porté à 210 "C sous agitation et à pression atmosphérique. On élimine la quasi-totalité de l'eau lors de la montée en température et par un stripping à l'azote. Puis on introduit le Forane 133a à un débit moyen de 40 g/h pendant 4 h.22.8 g (0.2 mole) of ε-caprolactone are charged to 289 g of DMI in the reactor. Then poured at room temperature 22.8 g of an aqueous solution of KOH a 49%. The reaction medium is brought to 210 ° C. with stirring and at atmospheric pressure. Almost all of the water is removed during the rise in temperature and by nitrogen stripping. Then the Forane 133a is introduced at a rate average 40 g / h for 4 h.
Le trifluoroéthanol formé distille au fur et à mesure de l'avancement de la réaction. Après 4h, le rendement en trifluoroéthanol par rapport à la potasse introduite est de 85%.The trifluoroethanol formed distills as the reaction progresses. After 4 hours, the yield of trifluoroethanol relative to the potassium introduced is 85%.
Exemple 3 :Example 3:
Dans cet exemple, la fabrication du trifluoroéthanol est effectuée comme dans l'Exemple 2 , mais avec remplacement de KOH par K2C03.In this example, the manufacture of trifluoroethanol is carried out as in Example 2, but with replacement of KOH by K 2 C0 3 .
Dans le réacteur, on charge 25,1 g (0,22 mole) d'ε-caprolactone dans 200 g de DMI. Puis on coule à la température ambiante 27,6 g d'une solution aqueuse de K2C03 à 50%. On porte le milieu réactionnel à 213 *C avec un léger débit d'azote pour éliminer l'eau. Une fois la température atteinte, on introduit le Forane 133a à un débit moyen de 40 g/h.25.1 g (0.22 mol) of ε-caprolactone are loaded into 200 g of DMI into the reactor. Then poured at room temperature 27.6 g of an aqueous solution of K 2 C0 3 at 50%. The reaction medium at 213 ° C with a slight nitrogen flow to remove water. Once the temperature has been reached, the Forane 133a is introduced at an average flow rate of 40 g / h.
Après 4h de réaction, on obtient un rendement en trifluoroéthanol de 74,5% par rapport au carbonate de potassium introduit.After 4 hours of reaction, a yield of trifluoroethanol of 74.5% is obtained relative to the potassium carbonate introduced.
Exemple 4 :Example 4:
Dans cet exemple, la fabrication du trifluoroéthanol est effectuée comme dans l'Exemple 1, mais en remplaçant le Forane 133a par le 2-bromo-1, 1, 1- trifluoroethane. On charge 35 g (0,205 mole) de 6-hydroxy- hexanoate de potassium dans 200 g de DMI. Le milieu réactionnel est porté à 210"C. Puis on introduit leIn this example, the manufacture of trifluoroethanol is carried out as in Example 1, but replacing Forane 133a with 2-bromo-1, 1, 1-trifluoroethane. 35 g (0.205 mol) of potassium 6-hydroxyhexanoate are loaded into 200 g of DMI. The reaction medium is brought to 210 ° C. Then the
2-bromo-1, 1, 1-trifluoroethane à un débit moyen de 36 g/h. Au bout de 2h de réaction, le rendement en trifluoroéthanol est de 74% par rapport au 6-hydroxy- hexanoate de potassium introduit.2-bromo-1, 1, 1-trifluoroethane at an average flow rate of 36 g / h. After 2 hours of reaction, the yield of trifluoroethanol is 74% relative to the potassium 6-hydroxyhexanoate introduced.
Exemple 5 :Example 5:
On procède comme dans l'Exemple 1, excepte qu'en fin de reaction, le milieu réactionnel est filtre pour récupérer le KC1 généré par la réaction. Le filtrat ainsi obtenu est réengagé sans traitement pour un autre essai . On ajoute à température ambiante une solution aqueuse de KOH (0,2 mole de KOH pour 11,7 g d'eau) , puis on opère comme dans l'Exemple 2. Le même milieu réactionnel a ainsi ete utilise pour cinq essais consécutifs A â E.The procedure is as in Example 1, except that at the end of the reaction, the reaction medium is filtered to recover the KC1 generated by the reaction. The filtrate thus obtained is reengaged without treatment for another test. An aqueous solution of KOH (0.2 mole of KOH for 11.7 g of water) is added at room temperature, then the procedure is as in Example 2. The same reaction medium was thus used for five consecutive tests A â E.
Les résultats obtenus sont rapportes dans le Tableau 1 suivant :The results obtained are reported in the following Table 1:
TABLEAU 1TABLE 1
Figure imgf000010_0001
Figure imgf000010_0001
Exemple 6 :Example 6:
Dans le montage standard des essais précédents, on charge 33,8 g (0,2 mole) de 6-aminohexanoate de potassium dans 289 g de DMI. Le 6-aminohexanoate de potassium est préparé indépendamment par action de la potasse sur l'e-caprolactame. Le milieu réactionnel est porté a 210 'C. Puis on injecte en continu le F133a à un débit moyen de 40 g/h.In the standard assembly of the preceding tests, 33.8 g (0.2 mole) of potassium 6-aminohexanoate are loaded into 289 g of DMI. Potassium 6-aminohexanoate is prepared independently by the action of potash on e-caprolactam. The reaction medium is brought to 210 ° C. Then the F133a is injected continuously at an average rate of 40 g / h.
Apres 2h30 de réaction, on obtient un rendement de 61% en trifluoroéthanol par rapport au sel de potassium de l'acide 6-aminohexanoιque engagé. After 2 h 30 of reaction, a 61% yield of trifluoroethanol is obtained relative to the potassium salt of the 6-aminohexanoιque acid used.

Claims

REVENDICATIONS
1 - Procédé de fabrication d'un composé de formule (I) :1 - Process for manufacturing a compound of formula (I):
Rf - CH2 - OH (I) dans laquelle Rf représente un radical alkyle perfluoré en cl~c10 ' caractérise par le fait que l'on fait reagir sous une pression comprise entre 0,10 et 2 bar, a une température deR f - CH 2 - OH (I) in which R f represents a perfluorinated alkyl radical in c l ~ c 10 ′ characterized in that one reacts under a pressure of between 0.10 and 2 bar, has a temperature of
100"C a 280 'C, dans un solvant aprotique polaire, un compose de formule (II) :100 " C at 280 ° C, in a polar aprotic solvent, a compound of formula (II):
Rf - CH2 - X (II) dans laquelle :R f - CH 2 - X (II) in which:
X représente un halogène ; et Rf est tel que défini ci-dessus, avec un sel de formule (III) :X represents a halogen; and Rf is as defined above, with a salt of formula (III):
OO
Figure imgf000012_0001
Figure imgf000012_0001
dans laquelle :in which :
1 o1 o
R1 et R représentent chacun indépendamment un atome d'hydrogène ou un groupe alkyle linéaire ou ramifie en C-^-C^, deux atomes de carbone voisins de l'enchaînement -(CR-'-R )m pouvant avec les radie ^x qu'ils portent faire partie d'un cycle aliphatique ou aromatique ; m = 3 , 4 ou 5 ; A représente 0 ou NH ; et M représente un métal alcalin, le composé de formule (II) étant introduit en continu dans le reacteur dans lequel on a préalablement introduit le compose (III) et le solvant aprotique polaire, et le compose (I) qui distille étant récupéré en continu au fur et a mesure de sa formation.R 1 and R each independently represent a hydrogen atom or a linear or branched C - ^ - C ^ alkyl group, two carbon atoms neighboring the chain - (CR -'- R) m being able with the radie ^ x they are part of an aliphatic or aromatic cycle; m = 3, 4 or 5; A represents 0 or NH; and M represents an alkali metal, the compound of formula (II) being introduced continuously into the reactor into which the compound (III) and the polar aprotic solvent, and the compound (I) which distills being continuously recovered as it is formed.
2 - Procède selon la revendication 1, caractérise par le fait que l'on conduit la reaction a la pression atmosphérique normale ou proche de la normale.2 - Process according to claim 1, characterized in that the reaction is carried out at normal atmospheric pressure or close to normal.
3 - Procède selon l'une des revendications 1 et 2 , caractérise par le fait que l'on conduit la reaction a une température comprise entre 120'C et 240 ' C . 4 - Procède selon l'une des revendications 1 a 3 , caractérise par le fait que l'on utilise, comme compose de formule (II), le 2-chloro-l,1, 1-trifluoroethane, le 2-bromo- 1, 1, 1-trifluoroethane, le 2-iodo-l, 1, 1-trifluoroethane.3 - Method according to one of claims 1 and 2, characterized in that the reaction is carried out at a temperature between 120'C and 240 'C. 4 - Method according to one of claims 1 to 3, characterized in that one uses, as compound of formula (II), 2-chloro-l, 1, 1-trifluoroethane, 2-bromo- 1 , 1, 1-trifluoroethane, 2-iodo-1, 1, 1-trifluoroethane.
5 - Procède selon l'une des revendications 1 a 4, caractérise par le fait qu'on utilise, comme sel (III) , un sel de potassium.5 - Method according to one of claims 1 to 4, characterized in that one uses, as salt (III), a potassium salt.
6 - Procède selon l'une des revendications 1 a 5, caractérise par le fait que l'on utilise comme compose (III) un sel de métal alcalin de l'acide 6-hydroxy (ou 6-amino) hexanoique ; de l'acide 4-hydroxy (ou 4-amino) butyrique ; de l'acide 5-hydroxy (ou 5-ammo) pentanoïque ; de l'acide 4-hydroxy (ou 4-amino) 4-ethyl butyrique ; et de l'acide 2-hydroxyméthyl benzoïque.6 - Method according to one of claims 1 to 5, characterized in that one uses as compound (III) an alkali metal salt of 6-hydroxy (or 6-amino) hexanoic acid; 4-hydroxy (or 4-amino) butyric acid; 5-hydroxy (or 5-ammo) pentanoic acid; 4-hydroxy (or 4-amino) 4-ethyl butyric acid; and 2-hydroxymethyl benzoic acid.
7 - Procède selon l'une des revendications 1 a 6, caractérise par le fait que l'on choisit le solvant aprotique polaire parmi le sulfolane, le N,N-dimethylformamide, le dimethylsulfoxyde, le N,N-dimethylacetamide, la N-méthylpyrrolidone, la 1, 3-dimethyl-2-imιdazolidmone, la 1, 3-dimethyl-3,4 , 5, 6-tetrahydro-2-pyrimidinone et leurs mélanges.7 - Method according to one of claims 1 to 6, characterized in that one chooses the polar aprotic solvent from sulfolane, N, N-dimethylformamide, dimethylsulfoxide, N, N-dimethylacetamide, N- methylpyrrolidone, 1, 3-dimethyl-2-imιdazolidmone, 1, 3-dimethyl-3,4, 5, 6-tetrahydro-2-pyrimidinone and their mixtures.
8 - Procède selon l'une des revendications 1 a 7, caractérise par le fait que l'on conduit la reaction avec un rapport molaire du composé de formule (II) au sel de formule (III) compris entre 0,5 et 10, de préférence entre 1 et 7.8 - Method according to one of claims 1 to 7, characterized in that the reaction is carried out with a molar ratio of the compound of formula (II) to the salt of formula (III) of between 0.5 and 10, preferably between 1 and 7.
9 - Procède selon l'une des revendications 1 a 8, caractérise par le fait qu'on opère a une concentration du sel de formule (III) comprise entre 5 et 40% en poids, de préférence entre 10 et 25% en poids par rapport au solvant aprotique polaire.9 - Method according to one of claims 1 to 8, characterized in that one operates at a concentration of salt of formula (III) of between 5 and 40% by weight, preferably between 10 and 25% by weight relative to the polar aprotic solvent.
10 - Procédé selon l'une des revendications 1 a 9, caractérisé par le fait que l'on engage dans la reaction un sel de formule (III) préalablement préparé.10 - Method according to one of claims 1 to 9, characterized in that one engages in the reaction a salt of formula (III) previously prepared.
11 - Procédé selon l'une des revendications 1 a 9 , caractérisé par le fait que l'on forme le sel de formule (III) in situ en engageant dans la réaction un compose de formule (IV) :11 - Method according to one of claims 1 to 9, characterized in that the salt of formula (III) is formed in situ by engaging in the reaction a compound of formula (IV):
Figure imgf000014_0001
Figure imgf000014_0001
dans laquelle A, R 1x et R9 sont tels que définis à la revendication 1 et une base.wherein A, R 1 x and R9 are as defined in claim 1 and a base.
12 - Procédé selon la revendication 11, caractérisé par le fait que l'on utilise comme compose (IV) l'e-caprolactone ou l'e-caprolactame ; la γ-butyrolactone ou le γ-butyrolactame ; la 6-valerolactone ou le r5-valero- lactame; la 4-éthylbutyrolactone ou le 4-éthylbutyrolactame; et le phtalide. 13 - Procédé selon l'une des revendications 1 a 12, caractérisé par le fait qu'après avoir récupéré le compose (I) et retiré du milieu réactionnel le sel forme MX (M et X étant tels que définis à la revendication 1) , on recycle le milieu réactionnel dans la même réaction en y ajoutant une base capable de former in situ le composé (III) . 12 - Process according to claim 11, characterized in that one uses as compound (IV) e-caprolactone or e-caprolactam; γ-butyrolactone or γ-butyrolactam; 6-valerolactone or r5-valero-lactam; 4-ethylbutyrolactone or 4-ethylbutyrolactam; and phthalide. 13 - Method according to one of claims 1 to 12, characterized in that after having recovered the compound (I) and removed from the reaction medium the salt forms MX (M and X being as defined in claim 1), the reaction medium is recycled in the same reaction by adding a base capable of forming the compound (III) in situ.
PCT/FR1996/001971 1995-12-12 1996-12-10 Method for making fluoroalkanols WO1997021656A1 (en)

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Cited By (3)

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Publication number Priority date Publication date Assignee Title
EP1426351A1 (en) * 2001-09-14 2004-06-09 Tosoh F-Tech, Inc. Process for preparation of 2,2,2-trifluoroethanol
CN108178723A (en) * 2017-12-19 2018-06-19 西安近代化学研究所 The synthetic method of 2,2- difluoroethanols
CN115636723A (en) * 2022-10-19 2023-01-24 浙江巨化技术中心有限公司 Preparation method of trifluoroethanol

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Publication number Priority date Publication date Assignee Title
GB2117376A (en) * 1982-02-04 1983-10-12 Onoda Cement Co Ltd Process for producing 2,2,2-trifluoroethanol
GB2123408A (en) * 1982-02-05 1984-02-01 Onoda Cement Co Ltd A process for producing fluorinated esters
EP0101526A1 (en) * 1981-03-23 1984-02-29 Halocarbon Products Corporation Process for the preparation of trifluoroethanol
JPS6169742A (en) * 1984-09-13 1986-04-10 Mitsubishi Metal Corp Production of fluorinated ester

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EP0101526A1 (en) * 1981-03-23 1984-02-29 Halocarbon Products Corporation Process for the preparation of trifluoroethanol
GB2117376A (en) * 1982-02-04 1983-10-12 Onoda Cement Co Ltd Process for producing 2,2,2-trifluoroethanol
GB2123408A (en) * 1982-02-05 1984-02-01 Onoda Cement Co Ltd A process for producing fluorinated esters
JPS6169742A (en) * 1984-09-13 1986-04-10 Mitsubishi Metal Corp Production of fluorinated ester

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1426351A1 (en) * 2001-09-14 2004-06-09 Tosoh F-Tech, Inc. Process for preparation of 2,2,2-trifluoroethanol
EP1426351A4 (en) * 2001-09-14 2006-03-01 Tosoh F Tech Inc Process for preparation of 2,2,2-trifluoroethanol
CN108178723A (en) * 2017-12-19 2018-06-19 西安近代化学研究所 The synthetic method of 2,2- difluoroethanols
CN115636723A (en) * 2022-10-19 2023-01-24 浙江巨化技术中心有限公司 Preparation method of trifluoroethanol
CN115636723B (en) * 2022-10-19 2023-12-19 浙江巨化技术中心有限公司 Preparation method of trifluoroethanol

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