EP1863752A1 - Procede de production d'acide 5-halo-2,4,6-trifluoroisophtalique - Google Patents

Procede de production d'acide 5-halo-2,4,6-trifluoroisophtalique

Info

Publication number
EP1863752A1
EP1863752A1 EP06725104A EP06725104A EP1863752A1 EP 1863752 A1 EP1863752 A1 EP 1863752A1 EP 06725104 A EP06725104 A EP 06725104A EP 06725104 A EP06725104 A EP 06725104A EP 1863752 A1 EP1863752 A1 EP 1863752A1
Authority
EP
European Patent Office
Prior art keywords
reaction
halo
isophthalonitrile
isophthalic acid
acid
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP06725104A
Other languages
German (de)
English (en)
Inventor
Michael Rack
Sebastian Peer Smidt
Manuel Budich
Volker Maywald
Michael Keil
Bernd Wolf
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF SE
Original Assignee
BASF SE
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by BASF SE filed Critical BASF SE
Publication of EP1863752A1 publication Critical patent/EP1863752A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C25/00—Compounds containing at least one halogen atom bound to a six-membered aromatic ring
    • C07C25/02—Monocyclic aromatic halogenated hydrocarbons
    • C07C25/13—Monocyclic aromatic halogenated hydrocarbons containing fluorine
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/23—Preparation of halogenated hydrocarbons by dehalogenation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/361—Preparation of halogenated hydrocarbons by reactions involving a decrease in the number of carbon atoms
    • C07C17/363—Preparation of halogenated hydrocarbons by reactions involving a decrease in the number of carbon atoms by elimination of carboxyl groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/08—Preparation of carboxylic acids or their salts, halides or anhydrides from nitriles

Definitions

  • the present invention relates to a process for the preparation of 5-halo-2,4,6-trifluoroisophthalic acid of the formula I 1
  • 5-halo-2,4,6-trifluoroisophthalic acid (I) is an intermediate in the synthesis of trifluorobenzene, an important building block for the production of drugs in the pharmaceutical and plant protection area.
  • US 4,647,411 discloses a method in which Tetrafluorisophthalodinitril in 70 wt% sulfuric acid at 157 to 162 ° C in 15 h with a yield of 95% to Tetrafluoroisophthalic acid is hydrolyzed.
  • 5-Chloro-2,4,6-trifluoroisophthalodinitrile according to Kogyo Kagaku Zasshi (1979), 73 (2), 447-8, reacts with 60% sulfuric acid under reflux within 5 hours to 78% in 5-chloro-2 , 4,6-trifluoroisophthalic acid.
  • EP-A 1 256 564 teaches that 5-chloro-2,4,6-trifluoroisophthalic acid is hydrolysed by 10 times the amount of reflux-heated, 62% sulfuric acid from 5-chloro-2 within 3 hours, 4,6-trifluoroisophthalonitrile is obtained in 95.4% yield.
  • the harsh reaction conditions of the disclosures US 4,647,411, Kogyo Kagaku Zasshi (1979), 73 (2), 447-8 and EP 1 256 564 are disadvantageous for industrial applications. At reaction temperatures of T> 150 0 C, as they are present at heated to reflux 62 wt .-% sulfuric acid, all common reactor materials are unstable.
  • the object of the present invention was to provide an economical and industrially applicable process for the preparation of 5-halo-2,4,6-trifluoroisophthalic acid.
  • the object of the present invention was in particular to provide a method for
  • X is halogen, ie fluorine, chlorine, bromine or iodine.
  • the process according to the invention is preferably used for the preparation of compounds in which X is chlorine or bromine; most preferably X is chlorine.
  • isophthalonitrile (II) or a solution thereof is added in a first step with concentrated sulfuric acid.
  • the isophthalonitrile (II) can be added to the concentrated sulfuric acid in solid form, for example, powdered or flaked. It is possible to bring the isophthalonitrile (II) dissolved or water-moist in the reaction.
  • isophthalonitrile (II) is used moist with water. Under moist water are residual water contents of preferably up to 40% by weight based on isophthalonitrile (II) to understand. More preferably, the compound of formula II is introduced with a water content of 30 to 35 wt .-% in the reaction.
  • a suspension is preferably prepared. Suspending means the most uniform distribution of the solid isophthalonitrile (II) in the concentrated sulfuric acid, e.g. by stirring.
  • the isophthalonitrile (II) can also be dissolved in a solvent, for example as a desired product from a preceding process step, introduced into the reaction.
  • solvents for example, aromatic solvents such as substituted or preferably unsubstituted alkylbenzenes, such as methylbenzene, dimethylbenzenes or
  • Trimethylbenzenes their mixtures of isomers or chlorobenzenes used. Particularly preferred is toluene.
  • concentrated sulfuric acid is used, generally using a concentration of at least 70% by weight.
  • Preferred is a
  • the amount of sulfuric acid in relation to the isophthalonitrile (II) is kept as low as possible and is generally less than 20 molar equivalents, for example from 3 to 20 molar equivalents, preferably from 4 to 10 molar equivalents, more preferably from 5 to 7 molar equivalents.
  • isophthalonitrile (II) or its solution are mixed at room temperature with the concentrated sulfuric acid.
  • the temperatures are above freezing, preferably at 10 ° C. or above.
  • the temperature range is particularly preferably 20 to 30 0 C.
  • both the isophthalonitrile (II) in solid (for example water-wet) or dissolved form and also the sulfuric acid can be initially charged.
  • the process according to the invention can be carried out under reduced pressure.
  • the pressure is generally chosen so that the solvent used can be easily removed, for example by distillation.
  • the reaction is preferably conducted so as to substantially avoid the sublimation of isophthalonitrile (II) in the reaction system, that is, in general, less than 0.5% by weight of the compound of formula II sublimate.
  • the sulfuric acid / isophthalonitrile (II) suspension or mixture is heated after complete addition of the isophthalonitrile (II).
  • the temperatures are preferably 110 ° C. or below.
  • a temperature range of 90 to 110 0 C has generally proved to be advantageous.
  • Particularly preferred is a temperature range of 90 to 100 0 C, particularly preferably of 95 to 100 0 C.
  • Isophthalodiamid (III) is formed as an intermediate.
  • the isophthalo-diamide (III) is partially formed. Reaction conditions in which the isophthalo-diamide (III) is formed almost quantitatively from the compound of the formula II are particularly preferred.
  • water is preferably added in such a way that the reaction mixture is not significantly heated by the exothermic reaction above the temperatures indicated below.
  • the temperatures are in the range of 90 to 140 0 C.
  • the reaction is particularly preferably carried out at temperatures of 115 to 125 ° C.
  • Water may be added to the reaction by, for example, pouring, dripping or spraying.
  • the temperature of the added water is not essential to the reaction; Both cold and hot water can be added to the reaction.
  • the hydrolysis to isophthalic acid (I) is usually carried out with 3 or more molar equivalents of water. In general, 25 molar equivalents of water are sufficient. Preference is given to 15 to 25 molar equivalents, more preferably 15 to 22 molar equivalents.
  • the reaction mixture is allowed to afterreact; It is stirred for example for a further 2 to 12 h at temperatures of 90 to 140 0 C.
  • a reaction temperature of generally 110 to 130 0 C is preferred. Particularly preferred are reaction temperatures from 115 to 125 0 C.
  • the reaction is continued until the reactant is substantially preferable have completely reacted, for example at least 95% of theoretical. This can for example already be reached after 6 hours.
  • the reaction also proceeds at higher temperatures, whereby experience has shown that the wear of the reactor material increases without any improvement in product quality being achieved.
  • reaction steps of the process according to the invention can be spatially separated or carried out in a reactor. They are preferably carried out in a reactor in the so-called one-pot process.
  • the process according to the invention can be carried out in such a way that isophthalamide (III) can be isolated.
  • Methods for isolating isophthalodiamide (III) are known per se to the person skilled in the art, or the isolation can also be carried out by methods known to the person skilled in the art.
  • the process according to the invention is preferably carried out in a one-pot process without isolation of the compound of the formula III up to the end product of the general formula I, 5-halo-2,4,6-trifluoroisophthalic acid.
  • the isophthalo-diamide (III) can also be used directly and hydrolyzed in dilute mineral acid to 5-halo-2,4,6-trifluoroisophthalic acid.
  • Sulfuric acid is preferably used in a concentration range of 30 to 80 wt .-%, particularly preferably 40 to 70 wt .-% sulfuric acid.
  • Isophthalodiamide (III) is usually hydrolyzed with 3 to 18 molar equivalents of sulfuric acid. Preferably 4 to 8 molar equivalents, more preferably 4 to 5 molar equivalents are used. Further preferred is a reaction temperature in the range of 110 to 130 0 C. More preferably, the reaction is carried out at temperatures of 115 to 125 0 C.
  • reaction mixture is stirred for 2 to 8 hours at temperatures of 115 to 125 ° C.
  • the reaction is continued until the reactants in the have preferably substantially fully implemented, for example, at least 95%. This can for example already be reached after 6 hours.
  • the compound of the formula I can be used as an intermediate starting from the compound of the formula II in a decarboxylation reaction for the preparation of 2-halo-1,3,5-trifluorobenzene of the formula IV, for example in EP-B 1 460 639 (Example 1 , Page 5, lines 32-47).
  • the decarboxylation is preferably carried out by heating the compound of general formula I in a polar solvent with or without the addition of catalysts at temperatures between 110 and 250 ° C.
  • the compound of the general formula IV can be used as an intermediate starting from the compound of the formula II in a dehalogenation reaction for the preparation of 1,3,5-trifluorobenzene of the formula V, for example in EP-B1 460 639 (Example 2, page 5 and example 3 , Page 6).
  • the dehalogenation is carried out by heating the compound of general formula IV in the presence of a metal and water under pressure at temperatures between 100 to 200 0 C.
  • the present process is characterized not only by the fact that it allows the gentle large-scale production of isophthalic acid (I), but also by the fact that the volume of required sulfuric acid is low. This is particularly advantageous with regard to the isolation of the desired product from the reaction mixture and the disposal of the residues. As a procedurally advantageous method of the invention may prove by the possibility of being able to bring the compound of formula II dissolved in a solvent in the reaction.
  • Example 1 197 g (0.88 mol) of 5-chloro-2,4,6-trifluoroisophthalodinitrile were suspended at room temperature in 624.5 g (6.37 mol) of 96% strength by weight H2SO4 in a glass round-bottomed flask and then taken up Heated to 100 ° C. There were added dropwise 327.6 g (18.18 mol) of water so that the reaction mixture warmed to 12O 0 C and then stirred for a further 8h at 120 0 C After cooling, the reaction mixture was stirred into 2000 ml of cold water, twice with 500 Methyl tert-butyl ether (MTBE) was extracted, and the combined organic phases dried and concentrated in vacuo. 228.1 g of 5-chloro-2,4,6-trifluoroisophthalic acid were obtained as a beige solid. Purity by 1 F NMR: 94% (96.2% of theory).
  • Example 2 197 g (0.88 mol) of 5-chloro-2,4,
  • Example 3 185,7g (1, 62 mol) of sulfuric acid (85 wt%) were charged and heated to 30 0 C. Then added dropwise under reduced pressure at 30-35 ° C, a solution of 50 g (0.46 mol) of 1-chloro-2,4,6-trifluoroisophthalonitrile in 100 ml of toluene. It continuously distilled off toluene. The reaction mixture was subsequently heated to 100 ° C. 61. 1 g (3.39 mol, 7.4 equivalents) of water were added. It was then heated to 130 ° C and stirred for 2h. After cooling to 60 ° C., first 150 ml of water were added. The fine suspension was extracted twice with 100 ml MTBE each time. The organic phases were combined, stirred with activated charcoal and sodium sulfate and filtered. The slightly yellowish organic phases were concentrated. 59 g of beige diacid (I) were obtained.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

Procédé de production d'acide 5-halo-2,4,6-trifluoroisophtalique de formule (I) dans laquelle X représente F, Cl, Br, ou I, par hydrolyse de 5-halo-2,4,6-trifluoroisophtalodinitrile de formule (II). Ledit procédé consiste à mettre en réaction lors d'une première étape de l'isophtalodinitrile (II) ou une solution contenant de l'isophtalodinitrile (II) avec de l'acide sulfurique concentré à température ambiante, ce qui permet d'obtenir du 5-haIo-2,4,6-trifluoroisophtalodiamide de formule générale (III), puis à chauffer le tout et dans une seconde étape à obtenir de l'acide isophtalique (I) après chauffe et ajout d'eau supplémentaires.
EP06725104A 2005-03-18 2006-03-16 Procede de production d'acide 5-halo-2,4,6-trifluoroisophtalique Withdrawn EP1863752A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102005013038 2005-03-18
PCT/EP2006/060793 WO2006097510A1 (fr) 2005-03-18 2006-03-16 Procede de production d'acide 5-halo-2,4,6-trifluoroisophtalique

Publications (1)

Publication Number Publication Date
EP1863752A1 true EP1863752A1 (fr) 2007-12-12

Family

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Family Applications (1)

Application Number Title Priority Date Filing Date
EP06725104A Withdrawn EP1863752A1 (fr) 2005-03-18 2006-03-16 Procede de production d'acide 5-halo-2,4,6-trifluoroisophtalique

Country Status (8)

Country Link
US (1) US20080146839A1 (fr)
EP (1) EP1863752A1 (fr)
JP (1) JP2008533099A (fr)
CN (1) CN101287695A (fr)
AR (1) AR053831A1 (fr)
BR (1) BRPI0608712A2 (fr)
IL (1) IL185217A (fr)
WO (1) WO2006097510A1 (fr)

Families Citing this family (2)

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Publication number Priority date Publication date Assignee Title
JP2010515706A (ja) * 2007-01-11 2010-05-13 ビーエーエスエフ ソシエタス・ヨーロピア アリール置換縮合ピリミジンの製造方法
CN111909035B (zh) * 2020-08-18 2024-01-16 周敏 一种降低废弃物排放的四氟对苯二酸的制备方法

Family Cites Families (14)

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Publication number Priority date Publication date Assignee Title
DE3338292A1 (de) * 1983-10-21 1985-05-02 Basf Ag, 6700 Ludwigshafen 7-amino-azolo(1,5-a)-pyrimidine und diese enthaltende fungizide
US4647411A (en) * 1984-11-06 1987-03-03 Nippon Shokubai Kagaku Kogyo Co., Ltd. 5,6,7,8-tetrafluoroanthraquinone derivatives
JPS62111942A (ja) * 1985-11-11 1987-05-22 Nippon Shokubai Kagaku Kogyo Co Ltd ３，４，５，６−テトラフルオロフタル酸の製法
DE3927888A1 (de) * 1989-08-24 1991-02-28 Philips Patentverwaltung Wechselrichteranordnung
JPH05230002A (ja) * 1992-02-20 1993-09-07 Nippon Light Metal Co Ltd テトラフルオロイソフタルアミド及びその製造方法並びにテトラフルオロイソフタル酸の製造方法
RU2147584C1 (ru) * 1995-10-27 2000-04-20 Американ Цианамид Компани Способ получения дигалоидазолопиримидинов и способ получения дигидроксиазолопиримидинов
US6117876A (en) * 1997-04-14 2000-09-12 American Cyanamid Company Fungicidal trifluorophenyl-triazolopyrimidines
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US6156925A (en) * 1998-09-25 2000-12-05 American Cyanamid Company Process for the preparation of halogenated phenylmaloates
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JP2002037757A (ja) * 2000-07-25 2002-02-06 Nippon Shokubai Co Ltd 含フッ素芳香族化合物およびその製造方法
UA76486C2 (en) * 2001-07-26 2006-08-15 Basf Ag 7-amino triazolopyrimidines, a process of praparation, a fungicidal preparations based thereon and a method to control phytopathogenic fungi
DE10223917A1 (de) * 2002-05-29 2003-12-11 Bayer Cropscience Ag Pyrazolopyrimidine
JP2006514676A (ja) * 2002-11-15 2006-05-11 ビーエーエスエフ　アクチェンゲゼルシャフト ２−メルカプト置換トリアゾロピリミジン類、それらを製造するための方法、病原性菌類を防除するためのそれらの使用、及び、２−メルカプト置換トリアゾロピリミジン化合物を含んでいる薬剤

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Also Published As

Publication number Publication date
JP2008533099A (ja) 2008-08-21
IL185217A (en) 2010-12-30
WO2006097510A1 (fr) 2006-09-21
BRPI0608712A2 (pt) 2010-12-07
AR053831A1 (es) 2007-05-23
US20080146839A1 (en) 2008-06-19
IL185217A0 (en) 2008-02-09
CN101287695A (zh) 2008-10-15

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