WO2015011718A1 - Procédé de distillation réactive pour la préparation de of 1, 1, 1, 2, 3, 3, 3-heptafluoro-2-bromopropane - Google Patents

Procédé de distillation réactive pour la préparation de of 1, 1, 1, 2, 3, 3, 3-heptafluoro-2-bromopropane Download PDF

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Publication number
WO2015011718A1
WO2015011718A1 PCT/IN2014/000389 IN2014000389W WO2015011718A1 WO 2015011718 A1 WO2015011718 A1 WO 2015011718A1 IN 2014000389 W IN2014000389 W IN 2014000389W WO 2015011718 A1 WO2015011718 A1 WO 2015011718A1
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WO
WIPO (PCT)
Prior art keywords
bromopropane
heptafluoro
preparation
reactive distillation
fluoride
Prior art date
Application number
PCT/IN2014/000389
Other languages
English (en)
Inventor
Sunil Sharma
Bhaskaran RAJGOPALAN
Rajdeep Anand
Hanuman GUPTA
Kapil Kumar
Rahul Saxena
Original Assignee
Srf Limited
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 Srf Limited filed Critical Srf Limited
Priority to EP14830166.6A priority Critical patent/EP3024807A4/fr
Publication of WO2015011718A1 publication Critical patent/WO2015011718A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/38—Separation; Purification; Stabilisation; Use of additives
    • C07C17/383—Separation; Purification; Stabilisation; Use of additives by distillation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/093—Preparation of halogenated hydrocarbons by replacement by halogens
    • C07C17/20—Preparation of halogenated hydrocarbons by replacement by halogens of halogen atoms by other halogen atoms
    • C07C17/202—Preparation of halogenated hydrocarbons by replacement by halogens of halogen atoms by other halogen atoms two or more compounds being involved in the reaction
    • C07C17/208—Preparation of halogenated hydrocarbons by replacement by halogens of halogen atoms by other halogen atoms two or more compounds being involved in the reaction the other compound being MX
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
    • C07C209/68—Preparation of compounds containing amino groups bound to a carbon skeleton from amines, by reactions not involving amino groups, e.g. reduction of unsaturated amines, aromatisation, or substitution of the carbon skeleton
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/10—Process efficiency

Definitions

  • the present invention provides a reactive distillation process for the preparation of 1 , 1, 1 , 2, 3, 3, 3-heptafluoro-2-bromoropane.
  • the 1 , 1 , 1 , 2, 3, 3, 3-heptafluoro-2-bromopropane is a key starting material for preparing polyhaloalkylated aromatics.
  • the polyhaloalkylated aromatics are becoming increasingly important, as lipophilic building blocks in agrochemical or pharmaceutical active ingredients.
  • the polyhaloalkyl substituents increase the lipophilicity and therefore the membrane permeability of the entire active ingredient molecule.
  • the US Publication Nos. 2004/0092762 and 2004/0092781 provide a process for the preparation of 1 , 1 , 1 , 2, 3, 3, 3-heptafluoro-2-bromopropane by heating dried mixture of tetramethylenesulphone and potassium fluoride with 1 , 2-dibromohexafluoropropane up to 175°C under nitrogen atmosphere and at a pressure of 13.5 bar.
  • the 1 , 1 , 1 , 2, 3, 3, 3-heptafluoro-2-bromopropane so obtained is allegedly 95.8 % pure.
  • the FR Patent Application No. 1357392 provides a process for the preparation of 1 , 1 , 1 , 2, 3, 3, 3-heptafluoro-2-bromopropane by heating a suspension of potassium fluoride and 1 , 2-dibromohexafluoropropane in N, N-dimethylformamide to about 90°C.
  • the 1, 1 , 1 , 2, 3, 3, 3-heptafiuoro-2-bromopropane is distilled into a cooled container. This process allegedly yields only 55% of 1 , 1 , 1 , 2, 3, 3, 3-heptafluoro-2-bromopropane over an elongated time period of 16 hours.
  • 753/DEL/2010 further discloses a process for the preparation of 4- heptafluoroisopropyl-2-methyl aniline by the reaction of ortho-toluidine with 1 , 1 , 1 , 2, 3, 3, 3-heptafluoro-2-bromopropane.
  • the present inventors have observed that the reaction did not proceed to completion when potassium fluoride and 1 , 2-dibromohexafiuoropropane were reacted in N, N- dimethyl form amide at about 90°C. Thus resulting in low yield of 1, 1 , 1 , 2, 3, 3, 3- heptafluoro-2-bromopropane. Further, 1 , 1 , 1 , 2, 3, 3, 3-heptafluoro-2-bromopropane was obtained in poor yield and low purity when potassium fluoride and 1 , 2- dibromohexafluoropropane were heated in N, N-dimethylformamide to about 140°C, cooled, decompressed and distilled.
  • the main object of the present invention is to provide a reactive distillation process for the preparation of 1 , 1 , 1 , 2, 3, 3, 3-heptafluoro-2-bromoropane.
  • the present inventors have found that the reactive distillation of 1 , 1 , 1 , 2, 3, 3, 3- heptafluoro-2-bromopropane by heating potassium fluoride and 1 , 2- dibromohexafluoropropane in N, N-dimethylformamide at a temperature in the range of about 90°C to about 150°C yields high and efficient output of 1 , 1 , 1 , 2, 3, 3, 3- heptafluoro-2-bromopropane without adhering to harsh reaction conditions like high temperature and pressure.
  • the reactive distillation of 1 , 1 , 1 , 2, 3, 3, 3-heptafluoro-2- bromopropane is particularly advantageous in a continuous mode wherein the simultaneous formation and continuous isolation/removal of 1 , 1 , 1 , 2, 3, 3, 3- heptafluoro-2-bromopropane from the reactive zone eliminates any side reactions thereby resulting in high yield and purity.
  • the "reactive distillation” comprises the simultaneous production and continuous isolation/removal of 1 , 1 , 1 , 2, 3, 3, 3-heptafluoro-2-bromopropane from the reactive zone.
  • the present invention provides a process for preparation of 1 , 1 , 1 , 2, 3, 3, 3-heptafluoro-2-bromopropane comprising; a) reacting 1, 2-dibromohexafiuoropropane and an alkali metal fluoride in presence of an amide solvent; and b) isolating 1 , 1 , 1 , 2, 3, 3, 3-heptafluoro-2-bromopropane by reactive distillation.
  • the present invention provides a process for preparation of 1 , 1 , 1 , 2, 3, 3, 3-heptafluoro-2-bromopropane comprising; a) reacting 1 , 2-dibromohexafiuoropropane and an alkali metal fluoride in presence of an amide solvent; and b) isolating 1 , 1 , 1 , 2, 3, 3, 3-heptafluoro-2-bromopropane by reactive distillation.
  • the alkali metal fluoride is selected from the group consisting of sodium fluoride, potassium fluoride and cesium fluoride or a mixture thereof.
  • the alkali metal fluoride may be in granular form or in powdered form.
  • the amide solvent is selected from the group consisting of N, N-dimethylformamide, methylpyrrolidone, N- methylformamide, dimethylacetamide, 2-pyrrolidone and N- vinylpyrrolidone or a mixture thereof.
  • the reaction of 1 , 2-dibromohexafluoropropane and an alkali metal fluoride is carried out at a temperature in the range of about 70°C to about 170°C, preferably in the range of about 90°C to about 150°C for a time period in the range of about 10 minutes to about 10 hours.
  • the 1 , 1 , 1 , 2, 3, 3, 3-heptafluoro-2-bromopropane is isolated by reactive distillation.
  • the reactive distillation is carried out at a temperature in the range of about 80°C to about 160°C, preferably in the range of about 90°C to about 150°C.
  • the 4-heptafluoroisopropyl-2-methyl aniline is prepared by the reaction of ortho-toluidine with 1 , 1 , 1 , 2, 3, 3, 3-heptafluoro-2-bromopropane, wherein 1 , 1 , 1 , 2, 3, 3, 3-heptafluoro-2-bromopropane is prepared by present invention.
  • Example 1 Preparation of 1 , 1 , 1 , 2, 3, 3, 3-Heptafluoro-2-bromopropane N, N-dimethylformamide (942 g), potassium fluoride (232 g) and 1 , 2- dibromohexafluoropropane (622 g) were taken together in a two-liter autoclave attached with one meter packed column. The column was maintained at atmospheric pressure. The temperature at the column head was maintained in the range of about 15°C to about 20°C. The reaction mixture was heated to about 90°C. The temperature of the reaction was increased slowly to about 140°C. The 1 , 1 , 1 , 2, 3, 3, 3-heptafluoro-2- bromopropane was distilled simultaneously and continuously from the top of the column for about 3 hours.
  • N, N-dimethylformamide (850 g), potassium fluoride (204 g) and 1 , 2- dibromohexafluoropropane (563 g) were taken together in a two-liter autoclave.
  • the temperature of the reaction mixture was increased slowly to about 140°C.
  • the reaction mixture was maintained at about 140°C for about 90 minutes.
  • the contents were cooled to 0°C and decompressed.
  • the 1 , 1 , 1 , 2, 3, 3, 3-heptaftuoro-2-bromopropane was distilled into the cold trap.

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

Abstract

La présente invention concerne un procédé de distillation réactive pour la préparation de 1, 1, 1, 2, 3, 3, 3-heptafluoro-2-bromoropane.
PCT/IN2014/000389 2013-07-26 2014-06-11 Procédé de distillation réactive pour la préparation de of 1, 1, 1, 2, 3, 3, 3-heptafluoro-2-bromopropane WO2015011718A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP14830166.6A EP3024807A4 (fr) 2013-07-26 2014-06-11 Procédé de distillation réactive pour la préparation de of 1, 1, 1, 2, 3, 3, 3-heptafluoro-2-bromopropane

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
IN2226DE2013 2013-07-26
IN2226/DEL/2013 2013-07-26

Publications (1)

Publication Number Publication Date
WO2015011718A1 true WO2015011718A1 (fr) 2015-01-29

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Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/IN2014/000389 WO2015011718A1 (fr) 2013-07-26 2014-06-11 Procédé de distillation réactive pour la préparation de of 1, 1, 1, 2, 3, 3, 3-heptafluoro-2-bromopropane

Country Status (2)

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EP (1) EP3024807A4 (fr)
WO (1) WO2015011718A1 (fr)

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB965643A (en) * 1962-05-21 1964-08-06 Dow Corning Improvements in or relating to fluorinated hydrocarbons
US20040092781A1 (en) * 2002-11-11 2004-05-13 Albrecht Marhold Preparation of polyhaloalkanes
CN102731317A (zh) * 2012-07-10 2012-10-17 中化蓝天集团有限公司 一种全氟烷基化苯胺衍生物的制备方法

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB965643A (en) * 1962-05-21 1964-08-06 Dow Corning Improvements in or relating to fluorinated hydrocarbons
US20040092781A1 (en) * 2002-11-11 2004-05-13 Albrecht Marhold Preparation of polyhaloalkanes
CN102731317A (zh) * 2012-07-10 2012-10-17 中化蓝天集团有限公司 一种全氟烷基化苯胺衍生物的制备方法

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP3024807A4 *

Also Published As

Publication number Publication date
EP3024807A1 (fr) 2016-06-01
EP3024807A4 (fr) 2017-03-15

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