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WO1987007267A1 - Procede de synthese du tetrafluorophtalonitrile - Google Patents

Procede de synthese du tetrafluorophtalonitrile Download PDF

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Publication number
WO1987007267A1
WO1987007267A1 PCT/US1986/002662 US8602662W WO8707267A1 WO 1987007267 A1 WO1987007267 A1 WO 1987007267A1 US 8602662 W US8602662 W US 8602662W WO 8707267 A1 WO8707267 A1 WO 8707267A1
Authority
WO
WIPO (PCT)
Prior art keywords
tetrafluorophthalonitrile
process according
purity
solvent
product
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.)
Ceased
Application number
PCT/US1986/002662
Other languages
English (en)
Inventor
David Nalewajek
George Donald Lockyer
Richard Elmer Eibeck
Michael Francis Pyszczek
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.)
Honeywell International Inc
Original Assignee
Allied Corp
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 Allied Corp filed Critical Allied Corp
Publication of WO1987007267A1 publication Critical patent/WO1987007267A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C255/00—Carboxylic acid nitriles
    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/347—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups
    • C07C51/363—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups by introduction of halogen; by substitution of halogen atoms by other halogen atoms

Definitions

  • Fig. 1 illustrates the gas chromatographic trace of pure tetrafluorophthalonitrile prepared in accordance with the invention using dimethylformamide as solvent.
  • Fig. 2 illustrates the gas chromatographic trace of pure tetrafluorophthalonitrile prepared in accordance with the invention using dimethylacetamide as solvent.
  • Fig. 3 illustrates the gas chromatographic trace of pure tetrafluorophthalonitrile prepared in accordance with the invention using N-methylpyrrolidinone as solvent.
  • Fig. 4 compares the gas chromatographic traces of pure tetrafluorophthalonitrile prepared in accordance with the invention curve "a" (4a) to that prepared by prior art method curve (4b).
  • Fig. 5 illustrates the gas chromatographic trace of pure tetrafluorophthalonitrile isolated after the hexane volume has been reduced.
  • the reactants tetrachlorophthalonitrile and potassium fluoride are heated together in the presence of an aprotic solvent in a flask or kettle depending on the quantity of product required. High pressure vessels such as an autoclave are not required.
  • the reaction is carried out in solvents chosen from the class of organic amides of general formula:
  • the mole ratio of reactants is also a variable and must be controlled to ensure a product of high purity and yield.
  • the mole ratio of potassium fluoride to tetrachlorophthalonitrile can vary from four to a large excess. The preferred operating ratios being from about 4 to 8.
  • Using potassium fluoride to tetrachlorophthalo ⁇ nitrile ratios in excess of eight moles per mole of chloronitrile has no appreciable effect. This is demonstrated in Table 1, wherein the reaction time and temperature were held constant and only the mole ratio of potassium fluoride to tetrachlorophthalonitrile was varied as indicated. Note the small change in product yield and purity.
  • alkanes include hexane, heptane, octane, dodecane and the like.
  • the slight yellow color which is present in the crude product can be removed by treating the hot hydrocarbon solution with activated carbon, filtering the hot hydro ⁇ carbon solution to remove the carbon and cooling the hycrocarbon-tetrafluorophthalonitrile solution to ambient temperature to precipitate the pure product as white needles exhibiting a melting point of 83-85°C (see Figure 1).
  • the bulk of the hydrocarbon which was distilled can be recycled in the process.
  • tetrachlorophthalonitrile and potassium fluoride can be heated for 1-3 hours at 130-150°C using N-roethylpyrrolidinone as solvent. After quenching the reaction in water and isolating the precipitated product by filtration, tetrafluorophthalonitrile is isolated in 76-78% yield with a minimum purity of 98.5%.
  • the only identifiable impurities as produced by the methods taught in this disclosure are the two isomers of chlorotrifluorophthalonitrile, 3- chloro-4,5,6-trifluorophthalonitrile and 4-chloro-3,5,6- trifluorophthalonitrile their combined concentration being ⁇ 0.5%.
  • the procedure disclosed in the Ishikawa reference yields the tetrafluoro ⁇ phthalonitrile which contains not only these two isomers in higher percentages (3.6%) but an additional impurity (2.3%) appearing at a retention time of 12.5 minutes. This impurity could not be successfully removed from the bulk of the tetrafluorophthalonitrile.
  • the crude product was dissolved in 2L of hexane and treated with lOg of activated carbon. After heating for 0.5 hours at 69°C, the solution was filtered hot to remove the carbon. The colorless hexane solution was cooled to ambient temperature to yield white crystals of tetrafluorophthalonitrile (29.9g, 83%) with a melting point of 83-85°C. The minimum purity of this material as determined by capillary GC analysis was 99.7%. The GC trace is depicted in Fig. 1.
  • the crude product was dissolved in 200 mL of hot hexane and treated with one gram of activated carbon, after heating for 0.5 hours at 69°C, the solution was filtered hot to remove the carbon.
  • the volume of hexane was reduced to 80 mL (80% reduction) by distillation.
  • the distillation flask was cooled to ambient temperature to precipitate the pure tetrafluorophthalonitrile as white needles. Yield: 2.86g (80%).
  • EXAMPLE 7 50g of crude tetrachlorophthalonitrile as prepared by Example 1 was dissolved in 800mL of hot. heptane. The yellow solution was treated with 5.0g of activated car- bon and the mixture maintained at 95°C for 0.5hr. The solution was filtered hot to remove the carbon. The colorless heptane solution was cooled to ambient temperature to yield 48g of pure tetrafluorophthalo ⁇ nitrile of 100% purity as determined by capillary GC analysis.
  • EXAMPLE 8 Anhydrous potassium fluoride (35g) and tetrachlorophthalonitrile (20g) were heated in 150mL of di ethylformamide for 1 hour at 135 ⁇ C. After the reaction period was over, the flask was cooled to 10°C and water added directly to the organic phase to induce precipitation of crude tetrafluorophthalonitrile. A total of 200mL of water was required. After stirring for an additional 0.5h, the light yellow needles were filtered and dried. A yield of 12.34g (86%) was obtained with a corresponding purity of >_ 98% as determined by capillary GC analysis.

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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)

Abstract

Procédé de préparation de composés de formule générale C6Fx(CN)y, où x et y sont des nombres entiers dont la somme est égale à 6. Ce procédé est particulièrement utile dans la synthèse de nitriles fluorés contenant au moins deux groupes cyano (y=2). Parmi les composés préférés préparés, le tétrafluorophtalonitrile est un produit intermédiaire important utilisé comme constituant de base dans l'industrie pharmaceutique. Dans le procédé ci-décrit, le tétrafluorophtalonitrile est préparé grâce à la réaction d'un composé chloré de formule générale C6Clx(CN)y où x et y sont des nombres entiers dont la somme est égale à 6. Plus spécifiquement, on fait réagir du tétrachlorophtalonitrile avec du fluorure de potassium dans un solvant aprotique pour préparer le tétrafluorophtalonitrile. Le fluoronitrile est produit avec un rendement d'au moins 80 % et une purité minimale de 98,5 %. Une seule recristallisation supplémentaire est nécessaire poru produire une substance présentant une pureté supérieure à 99,5 %. Dans une variante, le tétrafluorophtalonitrile brut est recristallisé à partir d'un solvant d'hydrocarbure d'alcane pour produire une substance présentant une pureté supérieure à 99,5 % et pouvant être utilisée directement comme produit intermédiaire. Ce procédé représente une solution économique pour la production de tétrafluorophtalonitrile à l'échelle industrielle.
PCT/US1986/002662 1986-05-19 1986-12-10 Procede de synthese du tetrafluorophtalonitrile Ceased WO1987007267A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US86466186A 1986-05-19 1986-05-19
US864,661 1986-05-19

Publications (1)

Publication Number Publication Date
WO1987007267A1 true WO1987007267A1 (fr) 1987-12-03

Family

ID=25343776

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US1986/002662 Ceased WO1987007267A1 (fr) 1986-05-19 1986-12-10 Procede de synthese du tetrafluorophtalonitrile

Country Status (1)

Country Link
WO (1) WO1987007267A1 (fr)

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5362909A (en) * 1984-06-04 1994-11-08 Bayer Aktiengesellschaft Process for the preparation of 3-chloro-2,4,5-trifluorobenzoyl chloride, 2,4,5-trifuluorobenzoyl fluoride, and 2,3,4,5-tetrahalogenobenzene derivatives
US5530158A (en) * 1984-06-04 1996-06-25 Bayer Aktiengesellschaft 2,4,5-trihalogeno- and 2,3,4,5-tetrahalogenobenzene derivatives
WO2002028822A3 (fr) * 2000-10-04 2003-03-27 Showa Denko Kk Procede relatif a l'elaboration de dicyanobenzene fluore
RU2246484C2 (ru) * 2000-10-04 2005-02-20 Шоува Денко К.К. Способ получения фторированного дицианбензола
US7132561B2 (en) 2000-10-04 2006-11-07 Showa Denko K.K. Process for producing fluorinated dicyanobenzene
US7585363B1 (en) 2008-10-29 2009-09-08 Eastman Kodak Company Method for preparing nanodispersions of fluorinated phthalocyanine pigments
US7628849B1 (en) 2008-10-29 2009-12-08 Eastman Kodak Company Fluorinated bis-(phthalocyanylaluminoxy)silyl pigments
US8277697B2 (en) 2008-10-29 2012-10-02 Global Oled Technology Llc Color filter element with improved colorant dispersion

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR1381223A (fr) * 1961-09-25 1964-12-14 Diamond Alkali Co Nouveaux dérivés téréphtaliques, leur préparation et leurs applications
US3975424A (en) * 1974-07-04 1976-08-17 Agency Of Industrial Science & Technology Method for manufacture of tetrafluoroterephthalonitrile
GB2122190A (en) * 1982-05-27 1984-01-11 Ici Plc Decarboxylation of halogenated benzoic acids or esters
EP0120575A1 (fr) * 1983-02-18 1984-10-03 Nippon Shokubai Kagaku Kogyo Co., Ltd Composés organiques fluorés

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR1381223A (fr) * 1961-09-25 1964-12-14 Diamond Alkali Co Nouveaux dérivés téréphtaliques, leur préparation et leurs applications
US3975424A (en) * 1974-07-04 1976-08-17 Agency Of Industrial Science & Technology Method for manufacture of tetrafluoroterephthalonitrile
GB2122190A (en) * 1982-05-27 1984-01-11 Ici Plc Decarboxylation of halogenated benzoic acids or esters
EP0120575A1 (fr) * 1983-02-18 1984-10-03 Nippon Shokubai Kagaku Kogyo Co., Ltd Composés organiques fluorés

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
CHEMICAL ABSTRACTS, Vol. 72, No. 25, 22 June 1970 (Columbus, Ohio, US) N. ISHIKAWA et al.: "Synthesis of Fluorinated Aromatic Monomers. IV. Fluorination of Tetrachlorophthalonitrile and Tetrachloroisophthalonitrile in Solvents", see page 12, Abstract No. 133351Y, & Kogyo Kagaku Zasshi 1970, 73 (2) 447-8 *

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5362909A (en) * 1984-06-04 1994-11-08 Bayer Aktiengesellschaft Process for the preparation of 3-chloro-2,4,5-trifluorobenzoyl chloride, 2,4,5-trifuluorobenzoyl fluoride, and 2,3,4,5-tetrahalogenobenzene derivatives
US5530158A (en) * 1984-06-04 1996-06-25 Bayer Aktiengesellschaft 2,4,5-trihalogeno- and 2,3,4,5-tetrahalogenobenzene derivatives
US5565614A (en) * 1984-06-04 1996-10-15 Bayer Aktiengesellschaft 2,4,5-trihalogeno-and 2,3,4,5-tetrahalogenobenzene derivatives
WO2002028822A3 (fr) * 2000-10-04 2003-03-27 Showa Denko Kk Procede relatif a l'elaboration de dicyanobenzene fluore
RU2246484C2 (ru) * 2000-10-04 2005-02-20 Шоува Денко К.К. Способ получения фторированного дицианбензола
US7132561B2 (en) 2000-10-04 2006-11-07 Showa Denko K.K. Process for producing fluorinated dicyanobenzene
US7585363B1 (en) 2008-10-29 2009-09-08 Eastman Kodak Company Method for preparing nanodispersions of fluorinated phthalocyanine pigments
US7628849B1 (en) 2008-10-29 2009-12-08 Eastman Kodak Company Fluorinated bis-(phthalocyanylaluminoxy)silyl pigments
WO2010053502A2 (fr) 2008-10-29 2010-05-14 Global Oled Technology Llc . Procédé de préparation de nanodispersions de pigments de phthalocyanine fluorée
US8277697B2 (en) 2008-10-29 2012-10-02 Global Oled Technology Llc Color filter element with improved colorant dispersion

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