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WO2016009214A1 - Procédé de préparation de 1,1,2,3-tétrachloropropène (1230xa), de 1,2,3,3-tétrachloropropène (1230xd) ou d'un mélange de ceux-ci - Google Patents

Procédé de préparation de 1,1,2,3-tétrachloropropène (1230xa), de 1,2,3,3-tétrachloropropène (1230xd) ou d'un mélange de ceux-ci Download PDF

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Publication number
WO2016009214A1
WO2016009214A1 PCT/GB2015/052061 GB2015052061W WO2016009214A1 WO 2016009214 A1 WO2016009214 A1 WO 2016009214A1 GB 2015052061 W GB2015052061 W GB 2015052061W WO 2016009214 A1 WO2016009214 A1 WO 2016009214A1
Authority
WO
WIPO (PCT)
Prior art keywords
process according
tca
preparation
mixture
chlorination
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/GB2015/052061
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English (en)
Inventor
Andrew Paul Sharratt
Emma Jane HODGSON
John Charles Mccarthy
Maxine DORAN
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.)
Mexichem UK Ltd
Orbia Advance Corp SAB de CV
Original Assignee
Mexichem UK Ltd
Mexichem Amanco Holding SA de CV
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 Mexichem UK Ltd, Mexichem Amanco Holding SA de CV filed Critical Mexichem UK Ltd
Publication of WO2016009214A1 publication Critical patent/WO2016009214A1/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
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/25—Preparation of halogenated hydrocarbons by splitting-off hydrogen halides from halogenated hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/35—Preparation of halogenated hydrocarbons by reactions not affecting the number of carbon or of halogen atoms in the reaction
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C21/00—Acyclic unsaturated compounds containing halogen atoms
    • C07C21/02—Acyclic unsaturated compounds containing halogen atoms containing carbon-to-carbon double bonds
    • C07C21/04—Chloro-alkenes

Definitions

  • the invention relates to a process for the preparation of 1 ,1 ,2,3-tetrachloropropene 1 ,2,3,3-tetrachloropropene or a mixture thereof.
  • the invention relates to a process for the preparation of a composition comprising 1 ,1 ,2,3-tetrachloropropene, 1 ,2,3,3-tetrachloropropene or a mixture thereof.
  • 1 ,1 ,2,3-tetrachloropropene is also known as HCC-1230xa or 1230xa.
  • 1 ,1 ,2,3-tetrachloropropene will be referred to as 1230xa.
  • 1 ,2,3,3-tetrachloropropene is also known as HCC-1230xd or 1230xd.
  • 1 ,2,3,3- tetrachloropropene can exist as the E or Z isomer.
  • 1 ,2,3,3-tetrachloropropene will be referred to as 1230xd when referring to the compound in general or to a mixture of the isomers or 1230xd(E) or 1230xd(Z) when referring to the specific isomer.
  • 1230xa and 1230xd are useful as synthetic intermediates from which a range of pharmaceutical and agrochemicals as well as various hydrofluoroolefins, such as 2,3,3,3-tetrafluoropropene and 1 ,3,3,3-tetrafluoropropene can be produced.
  • HCF-1234yf 2,3,3,3-tetrafluoropropene is also known as HCF-1234yf, R-1234yf or 1234yf.
  • Hydrofluorocarbon (HFC) products are widely used in many applications, including refrigeration, air conditioning, foam expansion, and as propellants for aerosol products including medical aerosol devices. Although HFC's have proven to be more climate friendly than chlorofluorocarbons and hydrochlorofluorocarbon products that they have replaced, it has been discovered that they exhibit an appreciable global warming potential.
  • HFO hydrofluoroolefin
  • GWP global warming potential
  • 1234yf has been identified as a candidate alternative refrigerant to replace 1 ,1 , 1 ,2- tetrafluoroethane (R-134a, hereinafter referred to as 134a) in certain applications, notably mobile air conditioning or heat pumping applications. Its GWP is about 4. Of the routes to 1234yf, two have emerged as being commercially significant.
  • the route starting from 1230xa is also relatively straight forward and may be considered to be the favoured route for commercial scale preparation.
  • 1234yf can also be prepared from 1230xd.
  • species such as 1230xa and 1230xd are considered difficult to synthesize with their production processes often requiring many sequential chlorination and dehydrochlorination steps with low yields, and/or the handling of toxic and/or expensive reagents, and/or the use of extreme conditions, and/or the production of toxic by- products, see for example CN 101955414, WO2011/065574, US2009/0030249 and WO2012/166393.
  • the present invention provides a process for the production of 1230xa, 1230xd or mixtures thereof by using 1 ,1 ,3-trichloroacetone (TCA) as the starting material.
  • TCA has a number of synthetic uses and is produced commercially by a number of companies including Wacker Chimie of Germany.
  • the present invention provides a process for the production of 1230xa, 1230xd or mixtures thereof comprising reacting TCA with a nucleophilic chlorinating agent.
  • Nucleophilic chlorinating agents that can be used in the present invention include, but are not limited to phosphorous pentachloride (PCIs), thionyl chloride and triarylphosphine dichlorides. Phosphorous pentachloride is preferred because it is readily available and has many existing applications.
  • the present invention also provides a process for the production of a composition comprising 1230xa, 1230xd or a mixture thereof by the chlorination of TCA with a nucleophilic chlorinating agent e.g. PCI5.
  • a nucleophilic chlorinating agent e.g. PCI5.
  • TCA reacts with the nucleophilic chlorinating agent e.g. PCI5, to initially form 240aa, which then proceeds to lose HCI resulting in the production of 1230xa or 1230xd or a mixture thereof.
  • Chlorinated acetone impurities in the TCA e.g. 1 ,3-dichloroacetone also react with the nucleophilic chlorinating agent to form chlorinated propanes, e.g. 1 ,2,2,3-tetrachloropropane (250aa), which then lose HCI to form precursors to 1230xa using the indirect sequence illustrated below:
  • the present invention provides the use of 1230xa prepared from the chlorination of TCA with a nucleophilic chlorinating agent in the preparation of 1234yf.
  • the chlorination reaction of TCA may be carried out batch-wise or continuously, preferably continuously.
  • Any suitable apparatus may be used, such as a static mixer, a tubular reactor, a stirred tank reactor or a stirred vapour-liquid disengagement vessel.
  • the apparatus is made from one or more materials that are resistant to corrosion, e.g. stainless steels, Hastelloy ® , Inconel ® , glass or glass lined vessels.
  • the product from the chlorination reaction may be subjected to one or more purification steps. The purification may be achieved, for example, by separation of the desired product or reagents by one or more distillation, condensation or phase separation steps and/or by scrubbing with water or aqueous base and drying with e.g. molecular sieves, zeolites or other desiccants. Any unreacted TCA can be recycled to the reactor where it will ultimately be converted to 1230xa, 1230xd or a mixture thereof.
  • the chlorination reaction typically converts at least about 50% of the starting TCA into 1230xa, 1230xd or a mixture thereof, preferably at least about 75%, for example about 90%.
  • the chlorination reaction TCA- 230xa, 1230xd or mixtures thereof with a nucleophilic chlorinating agent e.g. PCIs can be carried out in many ways but is typically carried out in the liquid phase. Given the various ways in which the reaction can be performed, for example batch or continuous reaction, a stirred reactor or trickle bed, a wide range of conditions can be employed to affect it.
  • a temperature of from about - 40 to 200 °C may be used, e.g. from about -25 to about 150 °C. Lower and higher temperatures can be used but at the expense of rate and selectivity i.e. ratio of desired product to by-products.
  • Preferred temperatures for liquid phase chlorination are from about 0 to about 180 °C, e.g. from about 50 to about 150 °C.
  • the reaction may be performed under different conditions to the liquid phase. For example, if the vapour phase reaction is performed at super-atmospheric pressure then higher temperatures would be expected. Conversely, if it was performed at sub-atmospheric pressure similar or even lower temperatures might be expected.
  • any suitable solvent may be used or the reaction can be conducted in the absence of solvent, i.e. solvent free.
  • suitable we mean a solvent in which the reactants dissolve or are miscible in.
  • the solvent should be stable to chlorination and should not react with either the reactants or products within the taught ranges of temperature, pressure etc. If a solvent is present it is preferred that the chlorination reaction is carried out in the absence of water. This means that preferably the solvent is not water or does not comprise water.
  • Suitable solvents include, but are not limited to, chlorohydrocarbons such as methylene chloride, chloroform and the like. In one embodiment, an excess of the TCA feedstock or the 1230xa and/or 1230xd product itself can be used as the solvent.
  • the chlorination reaction TCA->1230xa, 1230xd or a mixture thereof may be carried out at atmospheric, sub- or super-atmospheric pressure, preferably super-atmospheric pressure.
  • the chlorination may be carried out at a pressure of from about 0 to about 4 MPa (40 bara), such as from about 0.1 to about 3 MPa (1 to 30 bara), e.g. from about 0.1 to about 2 MPa (1 to 20 bara).
  • the TCA used in the process of the present invention is purified before reacting with a nucleophilic chlorinating agent, such as PCI5.
  • TCA may be purified using a modified process from CN 101768066, which comprises dissolving the TCA in a solvent that is a combination of a polar solvent and a non-polar solvent in a specified ratio and cooling the solution obtained in order to obtain purified crystals of TCA.
  • the polar solvents are selected from water, methanol, ethanol, n-propanol, isopropanol, methyl acetate or ethyl acetate and the non-polar solvents are selected from petroleum ether, pentanes, such as n-pentane, hexanes, such as n-hexane, cyclohexane, heptanes, such as n-heptane, benzene or toluene and the ratio of polar solvent to non-polar solvent is from 1 :1 to 1 : 10, such as 1 :2 to 1 :5.
  • the ratio of TCA:nucleophilic chlorinating agent e.g. PCI5 on a molar basis is suitably from about 0.1 :1 to about 40:1 , such as from about 1 : 1 to about 20: 1 , preferably from about 1 :1 to about 10: 1 , e.g. from 1.5: 1 to about 5: 1.
  • the TCA can also perform the role of a reaction solvent.
  • the reaction is conducted in the absence of water or any other species that may react with either the TCA, or the nucleophilic chlorinating agents, such as PCI5, or the 1230xa and/or 1230xd product.
  • the nucleophilic chlorinating agent e.g. PCI5
  • the nucleophilic chlorinating agent is typically used in an amount relative to the TCA such that the preferred ratios disclosed above are achieved.
  • the nucleophilic chlorinating agent e.g. PCI5
  • PCI5 nucleophilic chlorinating agent
  • the chlorination reaction is typically conducted for a defined period, for example from 1 to 1000 hours, such as from about 10 to about 500 hours, e.g. from about 20 to about 200 hours. It is preferred that the chlorination reaction is conducted for a period of from about 30 to about 90 hours.
  • the chlorination reaction is typically conducted for a defined period, for example from 1 to 1000 hours, such as from about 1 to about 500 hours, e.g. from about 1 to about 20 hours.
  • the chlorination reaction is exothermic.
  • the exotherm that accompanies the reaction can be managed by controlling the rate at which the reaction occurs and removing the heat of reaction.
  • the heat of reaction can be removed by normal means such as applying cooling either internally or externally. Heat can also be removed by allowing the solvent to boil, condense and return to the reactor cold.
  • the present invention also provides a process for the preparation of 1230xa, 1230xd or mixtures thereof comprising the steps of;
  • the present invention provides a process for the preparation of 1230xa, 1230xd, or mixtures thereof which further comprises purifying the TCA before step (i).
  • the present invention also provides a process for the preparation of 1234yf comprising converting 1230xa to 1234yf, wherein the 1230xa is obtained using the process of the invention.
  • the present invention also provides the use of 1230xa in the preparation of 1234yf, wherein the 1230xa is obtained using the process of the invention.
  • the present invention also provides a process for the preparation of 1234yf comprising: i. converting 1230xa to 1233xf, wherein the 1230xa is obtained using the process of the invention;
  • the present invention also provides a process for preparing 1234yf which comprises a process of the invention and the additional step of converting 1230xa to 1234yf.
  • the present invention also provides a process for the production of 1230xa, 1230xd or mixtures thereof, in which 240aa is isolated as an intermediate and the 240aa is then converted into 1230xa, 1230xd or a mixture thereof.
  • 240aa is isolated as an intermediate and the 240aa is then converted into 1230xa, 1230xd or a mixture thereof.
  • the reaction conditions can be adjusted to favour regioselective loss of HCI from the 240aa molecule to favour particular isomers during its onward conversion to 1230xa, 1230xd or a mixture thereof.
  • the present invention also provides a process for preparing at least one hydrofluoroolefin comprising converting 1230xd to at least one hydrofluoroolefin, such as at least one hydrofluoropropene, e.g. 1234yf, wherein the 1230xd is obtained using the process of the invention.
  • the present invention also provides the use of 1230xd in the preparation of at least one hydrofluoroolefin, such as at least one hydrofluoropropene, e.g. 1234yf, wherein the 1230xa is obtained using the process of the invention.
  • the present invention also provides a process as described in Example 2 or Example 3.
  • the nucleophilic chlorinating agent is PCI5.
  • the process of the invention is conducted in the liquid phase.
  • the process of the invention is conducted at a temperature of from about 100 °C to about 180 °C.
  • Example 1 Purification of 1 , 1 ,3-trichloroacetone (TCA) (purchased from Sigma Aldrich) TCA was taken up in either 1 :5 methyl acetate :hexane or 1 :2 ethyl acetate: petroleum ether according to the method published in CN 101768066 and then cooled to -15°C in a bath of glycol/dry CO 2 while stirring. After 2 h of cooling and stirring, the solution was filtered under vacuum through a sintered funnel that had been pre-cooled in the freezer to yield crystals of TCA.
  • TCA 1 , 1 ,3-trichloroacetone
  • Example 2 Process for the preparation of 1230xa, 1230xd or a mixture thereof from purified 1 ,1 ,3-trichloroacetone (TCA) (85% purity)
  • Example 3- A Process for the preparation of 1230xa, 1230xd or a mixture thereof from 1 ,1 ,3-TCA (as supplied - 74% purity)

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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

Cette invention concerne un procédé de préparation de 1,1,2,3-tétrachloropropène (1230 xa), de 1,2,3,3-tétrachloropropène (1230 xd) ou d'un mélange de ceux-ci. Selon un autre aspect, l'invention concerne un procédé de préparation d'une composition comprenant du 1,1,2,3-tétrachloropropène (1230 xa), du 1,2,3,3-tétrachloropropène (1230 xd) ou un mélange de ceux-ci.
PCT/GB2015/052061 2014-07-17 2015-07-16 Procédé de préparation de 1,1,2,3-tétrachloropropène (1230xa), de 1,2,3,3-tétrachloropropène (1230xd) ou d'un mélange de ceux-ci Ceased WO2016009214A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB1412743.5 2014-07-17
GB1412743.5A GB2528310A (en) 2014-07-17 2014-07-17 Process

Publications (1)

Publication Number Publication Date
WO2016009214A1 true WO2016009214A1 (fr) 2016-01-21

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PCT/GB2015/052061 Ceased WO2016009214A1 (fr) 2014-07-17 2015-07-16 Procédé de préparation de 1,1,2,3-tétrachloropropène (1230xa), de 1,2,3,3-tétrachloropropène (1230xd) ou d'un mélange de ceux-ci

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WO (1) WO2016009214A1 (fr)

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011065574A1 (fr) * 2009-11-27 2011-06-03 Daikin Industries, Ltd. Procédé de synthèse de 1,1,2,3-tétrachloropropène
US20120059202A1 (en) * 2007-06-27 2012-03-08 Arkema Inc. Process for the manufacture of hydrofluoroolefins

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4535194A (en) * 1983-07-06 1985-08-13 Monsanto Co. Process for producing 1,1,2,3-tetrachloropropene
US5811605A (en) * 1997-02-19 1998-09-22 Ppg Industries, Inc. Preparation of 1,2,3,3-tetrachloropropene

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20120059202A1 (en) * 2007-06-27 2012-03-08 Arkema Inc. Process for the manufacture of hydrofluoroolefins
WO2011065574A1 (fr) * 2009-11-27 2011-06-03 Daikin Industries, Ltd. Procédé de synthèse de 1,1,2,3-tétrachloropropène

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
PAUL FRITSCH: "Ueber die Umwandlung des Pentachloracetons in Trichloracrylsäure und Monochlormalonsäure", JUSTUS LIEBIGS ANNALEN DER CHEMIE, vol. 297, no. 3, 1897, WEINHEIM; DE, pages 312 - 322, XP055212524, ISSN: 0075-4617, DOI: 10.1002/jlac.18972970304 *
S. LEVY ET AL: "Ueber symmetrisches Tetrachloraceton", JUSTUS LIEBIGS ANNALEN DER CHEMIE, vol. 252, no. 3, 1889, WEINHEIM; DE, pages 330 - 343, XP055212523, ISSN: 0075-4617, DOI: 10.1002/jlac.18892520307 *

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GB201412743D0 (en) 2014-09-03
GB2528310A (en) 2016-01-20
GB2528310A8 (en) 2016-02-17

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