WO1993024433A1 - Procede de production d'un hydrofluorocarbure possedant au moins un groupe trifluoro - Google Patents

Procede de production d'un hydrofluorocarbure possedant au moins un groupe trifluoro Download PDF

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Publication number
WO1993024433A1
WO1993024433A1 PCT/US1993/005282 US9305282W WO9324433A1 WO 1993024433 A1 WO1993024433 A1 WO 1993024433A1 US 9305282 W US9305282 W US 9305282W WO 9324433 A1 WO9324433 A1 WO 9324433A1
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matter
composition
formula
alkyl
catalyst
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PCT/US1993/005282
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English (en)
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Michael Van Der Puy
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Allied-Signal Inc.
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Publication of WO1993024433A1 publication Critical patent/WO1993024433A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C22/00—Cyclic compounds containing halogen atoms bound to an acyclic carbon atom
    • C07C22/02—Cyclic compounds containing halogen atoms bound to an acyclic carbon atom having unsaturation in the rings
    • 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
    • C07C17/26—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton
    • C07C17/272—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton by addition reactions
    • C07C17/275—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton by addition reactions of hydrocarbons and halogenated hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/26—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton
    • C07C17/272—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton by addition reactions
    • C07C17/278—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton by addition reactions of only halogenated hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C19/00—Acyclic saturated compounds containing halogen atoms
    • C07C19/08—Acyclic saturated compounds containing halogen atoms containing fluorine
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C19/00—Acyclic saturated compounds containing halogen atoms
    • C07C19/08—Acyclic saturated compounds containing halogen atoms containing fluorine
    • C07C19/10—Acyclic saturated compounds containing halogen atoms containing fluorine and chlorine
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
    • C07C2601/16—Systems containing only non-condensed rings with a six-membered ring the ring being unsaturated

Definitions

  • partially fluorinated organic compounds particularly those containing at least one trifluoro group
  • Such compounds find use in a variety of applications including pharmaceutical and agricultural intermediates.
  • interest in hydrofluorocarbons has increased because of their potential use as stratospherically safe materials for use as solvents, refrigerants, blowing agents, and sterilant gases.
  • HFCs hydrofluorocarbons
  • HCFC hydrochlorofluorocarbon
  • CFC chlorofluorocarbon
  • DE 3,917,573 discloses the preparation of 1,1,1,2-tetrafluoroethane by the selective hydrogenation of l,l-dichloro-l,2,2,2,- tetrafluoroethane in the presence of a Pd on alumina catalyst. Selective hydrogenation of HCFCs having more than two carbons, or of non-primary chlorines is not disclosed. Many HFCs containing at least one trifluoromethyl group have no commercially available HCFC counterparts.
  • R is hydrogen or a lower alkyl group
  • R 1 is lower alkyl
  • X is chloro, bromo or iodo
  • Y is fluoro, chloro or bromo
  • Z is ⁇ or Q
  • Q is a group of formula W(CF 2 )_ .
  • is hydrogen, fluoro or chloro and m is 1 or 2, provided that X is always bromo or iodo when at least one of Y and Z is bromo.
  • the present invention relates to a process for the reductive dechlorination of a hydrochlorofluorocarbon having at least three carbons, at least one trifluoromethyl group and at least one non-primary chlorine hydrochlorofluorocarbon in the presence of a catalyst selected from platinum, palladium and rhodium to produce a hydrofluorocarbon in a single step under neutral conditions.
  • the present invention further relates to a two step process wherein the hydrochlorofluorocarbon to be reductively dehalogenated is synthesized by reacting an olefin with 1,1,1- trichlorotrifluoroethane. Also disclosed are novel addition products having the general formula: H Cl
  • I I CF 3 -CC1 2 -C-C-Y I i Z X wherein Z is selected from H and lower alkyl, X is selected from H, alkyl, alkenyl, halogenated alkyl and halogenated alkenyl, Y is selected from alkyl, alkenyl, halogenated alkyl and halogenated alkenyl, and where Z and X are H, Y is not isopropyl or hexyl.
  • Hydrochlorofluorocarbons which may be reductively dechlorinated according to the present invention comprise at least three carbons, at least one trifluoro group and at least one non primary chlorine.
  • a non- primary chlorine is one which is bonded to a non ⁇ terminal carbon.
  • the hydrochlorofluorocarbon has at least 4 carbon atoms. More preferably the hydrochorofluorocarbon has between 4 and 25 carbon atoms and most preferably between 4 and 15 carbons.
  • the hydrochlorofluorocarbons may be straight chained, branched, or cyclic and may have any substitution on the main chain which does not interfere with, and is reduced by the reductive dechlorination, such as H, saturated or unsaturated hydrocarbyl or halohydrocarby1 , saturated or unsaturated hydroxy, carbonyl, cyano or nitro groups.
  • the reductive dechlorination is carried out in the presence of a catalyst comprising a metal selected from the group comprising platinum, palladium, and rhodium on an inert supj -rt.
  • a catalyst comprising a metal selected from the group comprising platinum, palladium, and rhodium on an inert supj -rt.
  • the metal is deposited on the support as an oxide or a salt.
  • the catalyst may be pretreated with hydrogen or used without pretreat ent.
  • the metal oxide or salt is converted to the metal via the pretreatment and during use.
  • the support may be carbon granules, alumina or any other support may be carbon granules, alumina or any other form generally practical in flow systems.
  • palladium over carbon is preferred over Pt/C.
  • Commercially available Pd/C is available at concentrations ranging from about 0.5% to 10% by weight palladium.
  • the chlorofluorocarbon and H 2 are passed over the catalyst. At least 3 moles of H 2 per mole chlorofluorocarbon are required by the reaction stoichiometry. Preferably an excess is used. Most preferably, about 9 moles of H 2 per 1 mole chlorofluorocarbon is used.
  • Hydrogen is used in excess of the stoichiometric requirement of 3 moles hydrogen per mole of chlorofluorocarbon, to increase conversion, and may be adjusted as necessary to control the residence time in the reactor.
  • the residence time depends on the reaction temperature; as the reactor temperature decreases the residence time required to insure complete reaction increases. Generally residence times between 1 and 60 seconds are sufficient.
  • the reductive dehalogenation of the present invention replaces all of the chlorines in the chlorofluorocarbon without reducing any of the fluorines.
  • environmentally undesirable HCFCs containing at least one trifluoro group may be selectively reduced to non-ozone depleting HFCs containing at least one trifluoromethyl group in a single step.
  • Unsaturated substituents may be saturated, oxygen may be replaced with hydrogen and nitriles may be converted to amines.
  • the resulting HFCs containing at least one trifluoromethyl group and have utility as non-ozone depleting refrigerants, sterilant gases, blowing agents and solvents.
  • Hydrochlorofluorocarbons which may be dechlorinated via the present invention may be made via any method known in the art.
  • HCFCs may be made by reacting an olefin with 1,1,1- trichlorotrifluoroethane (HCFC-113a) .
  • Olefins can be straight chain, branched or cyclic.
  • the reaction between the olefin and 1,1,1- trichlorotrifluoroethane is carried out in a suitable solvent.
  • Any solvent may be used so long as all of the reactants are soluble therein.
  • Suitable solvents include lower alcohols, nitriles and dimethylforma ide.
  • Preferred solvents are t-butanol, isopropanol, acetonitrile and 1,1,1-trichlorotrifluoroethane.
  • the preferred solvent for olefins having four carbons is t- butanol.
  • Various catalysts may be used for the addition of 1,1,1-trichlorotrifluoroethane to substituted and unsubstituted olefins.
  • the catalyst is a metal salt such as cuprous/cupric salts or ferrous/ferric salts. Copper salts are the more preferred catalysts, with CuCl being most preferred. Mixtures of copper salts may also be used, with equal weight mixtures of CuCl and cupric chloride dihydrate being preferred. Usually between about 1:100 to about 1:10 catalyst to olefin mole ratio is necessary to insure production of the desired chlorofluorocarbon. Preferably the catalyst to olefin mole ratio is about 1:50.
  • Amine co-catalysts may also be added to the reaction mixture.
  • Suitable amine co-catalysts include butylamine, N,N-dimethylethylene-diamine and ethanolamine with ethanolamine being especially preferred.
  • Conditions vary with the olefin used, since the reaction rates differ. Generally the reaction is monitored by the decrease in pressure of the system. Temperature limits vary with the solvent. For example temperatures below about 120*C are preferred for reactions in t-butanol; while temperatures up to about 170"C and higher can be used for reactions in acetonitrile. Temperatures between about 50 ⁇ C and about 100° are preferred.
  • the HCFC produced may be isolated by any common purification means known in the art such as extraction with a suitable solvent.
  • Hydrochlorofluorocarbons are useful intermediates for the production of reduced and non-ozone depleting HFCs which have utility as non- ozone depleting refrigerants, sterilant gases, blowing agents and solvents.
  • Example 1
  • a 300 mL glass pressure bottle was charged with 0.5 g of catalyst (50:50 weight mixture of CuCl and CuCl 2 «H 2 0) , 75 mL t-butanol, 3.0 g ethanolamine, and 50 g CF3CCI3, and evacuated briefly. Isobutylene (14.6 g) was then added, and the contents heated with an oil bath to and maintained at 85'C for 2 1/2 days. At this time the pressure in the vessel was 0 psig (lxlO 3 kPa) . The cooled reaction mixture was poured into 200 L water and the lower organic layer separated.
  • the aqueous layer was extracted with two 50 mL portions of CH 2 C1 2 , and the combined organic layers were washed with two 100 mL portions of water. After drying in Na 2 S0 ⁇ , the volatiles were removed by rotary evaporation. Vacuum distillation (6" packed column) of the residue gave 44.4 g of a colorless liquid having a boning point of 78-82 * C at 52 mm Hg. Elemental analysis calculated for C 6 H ⁇ Cl 3 F 3 is C, 29.60; H, 3.31 %. The elemental analysis for the reaction product was: C, 29.59; H, 3.20%. Thus, the recovered product was shown to be 1,1,l-trifluoro-2,2,4-trichloro-4- methylpentane (98 % purity) , which was confirmed by NMR analysis.
  • the hydrogenation reactor used in this example was a 1 inch glass tube having an internal volume of approximately 100 cc. Heat was applied by electrical heating tape wrapped around the outside of the tube. The tube was mounted vertically and packed with small glass rings in the lower one-third of the tube, followed by 25 cc of a mixture of 0.5% platinum on carbon (4 to 7 mesh, 10 cc) , 3 mm glass helices (15 cc) and the remainder of the tube was packed with glass rings. The reactor exit was connected to two dry- ice/acetone baths and a water scrubber. The reactor was purged with N 2 , heated to about 230 ⁇ C near the center of the reactor (skin temperature) and then purged with H 2 .
  • Example 1 The 1,1,1-trifluoro-2,2,4-trichloro-4- methylpentane produced in Example 1 was fed into the top of the reactor by means of a syringe pump at a rate of 1 cc every 9 minutes (total 32.6 g) .
  • the reactor temperature increased to about 250"C, and was maintained at about 250 ⁇ C throughout the dechlorination.
  • the hydrogen flow rate was adjusted to maintain a slow bubble rate in the water scrubber to insure that an excess of hydrogen is present.
  • the gas flow was maintained for one half hour. After warming the cold traps to room temperature, 14.9 g crude product was collected.
  • the product was analyzed via gas chromatography and found to be about 87 % 1,1,1- trifluoro-4-methylpentane and about 5% under-reduced (monochlorinated) material. Distillation of the 1,1,1- trifluoro-4-methylpentane gave 10.6 g (57%) of 1,1,1- trifluoro-4-methylpentane (99% purity) , having a boiling point of about 65-7 ⁇ C. The composition was confirmed via NMR.
  • Example 4 The product of Example 3 (36.5 g) was hydrogenated as in Example 2 to give 17.7 g crude product which from GC analysis was determined to be comprised of 42% of 1,1,1-trifluoro-3-methylpentane and 40% under-reduced material (but essentially no trichlorinated material) . Distillation gave 5 g pure product, having a boiling point of about 64-7 ⁇ C (mainly 66 ⁇ C) . The presence of 1,1,1-trifluoro-3-methylpentane was confirmed by NMR analysis.
  • a glass pressure bottle was charged with 1.0 g 1:1 (wt) CuCl:CuCl 2 *2H 2 0, 3.0 g ethanolamine, 55 g CF 3 CC1 3 and 75 mL t-butanol, and evacuated briefly. 1-Butene (16.7 g) was then added and the mixture stirred and heated to 85 * C for 15 hours, at which time the pressure in the vessel was 0 psig. The solution was extracted and dried as in Example 1.
  • the reactor in this Example was similar to that described in Example 2, except that 10 cc of 1% palladium on (4-8 mesh) carbon was used instead of platinum on carbon, and the temperature was measured internally using a thermocouple in the center of the catalyst bed.
  • a total of 40.7 g of the 1,1,1- trifluoro-2,2,4-trichlorohexane produced in Example 5 was passed over the bed with hydrogen gas over a period of 4 2/3 hours.
  • the temperature inside the reactor was 220*C before the organic flow was started, but increased to 244*C with organic and hydrogen passing over the catalyst bed. It was determined by GC analysis that the crude product consisted of 86 % of 1,1,1-trifluorohexane and about 12% under-reduced material.
  • Example 10 A mixture of 25 mL (39.6 g, 0.211 ol) CF 3 CC1 3 , 75 mL t-BuOH, 0.5 g of a 1:1 mixture of CuCl:CuCl 2 « 2H 2 0, 3 g ethanolamine, and 29.2 g (0.214 mol) li onene were heated to 70-75 *C for 4.5 days. Workup as in the previous examples gave 59.9 g crude material.

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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

L'invention se rapporte à un procédé servant à la déchloruration par réduction d'un hydrochlorofluorocarbure possédant au moins un groupe trifluorométhyle et au moins un chlore en présence d'un catalyseur sélectionné à partir de platine, palladium et rhodium, de façon à obtenir un hydrofluorocarbure en une seule étape dans des conditions neutres. L'invention se rapporte, de plus, à un procédé en deux étapes selon lequel l'hydrochlorofluorocarbure devant être déshalogéné par réduction est synthétisé au moyen de la réaction d'une oléfine avec 1,1,1-trichlorotrifluoroéthane, ainsi qu'aux nouveaux additifs fabriqués au moyen dudit procédé.
PCT/US1993/005282 1992-06-03 1993-06-02 Procede de production d'un hydrofluorocarbure possedant au moins un groupe trifluoro WO1993024433A1 (fr)

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US89316092A 1992-06-03 1992-06-03
US893,160 1992-06-03

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2030132A (en) * 1978-05-25 1980-04-02 Ici Ltd Polyhalogenated hydrocarbons, useful as insecticide intermediates, and methods for their preparation
WO1985002519A1 (fr) * 1983-12-07 1985-06-20 Fmc Corporation Fluoroalcanes et fluoroalcenes biocides
DE3712304A1 (de) * 1986-04-10 1987-10-15 Ceskoslovenska Akademie Ved Verfahren zur herstellung halogenierter organischer verbindungen
WO1991005752A1 (fr) * 1989-10-10 1991-05-02 E.I. Du Pont De Nemours And Company Hydrogenolyse d'halocarbones
EP0442087A1 (fr) * 1990-02-14 1991-08-21 Bayer Ag Procédé pour la fabrication d'hydrocarbures fluorés saturés sans chlore
EP0539989A1 (fr) * 1991-11-01 1993-05-05 Hoechst Aktiengesellschaft Procédé pour préparer 1,1,1,2,3,3,3-heptafluoropropane (R 227)

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2030132A (en) * 1978-05-25 1980-04-02 Ici Ltd Polyhalogenated hydrocarbons, useful as insecticide intermediates, and methods for their preparation
WO1985002519A1 (fr) * 1983-12-07 1985-06-20 Fmc Corporation Fluoroalcanes et fluoroalcenes biocides
DE3712304A1 (de) * 1986-04-10 1987-10-15 Ceskoslovenska Akademie Ved Verfahren zur herstellung halogenierter organischer verbindungen
WO1991005752A1 (fr) * 1989-10-10 1991-05-02 E.I. Du Pont De Nemours And Company Hydrogenolyse d'halocarbones
EP0442087A1 (fr) * 1990-02-14 1991-08-21 Bayer Ag Procédé pour la fabrication d'hydrocarbures fluorés saturés sans chlore
EP0539989A1 (fr) * 1991-11-01 1993-05-05 Hoechst Aktiengesellschaft Procédé pour préparer 1,1,1,2,3,3,3-heptafluoropropane (R 227)

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
COLLECTION OF CZECHOSLOVAK CHEMICAL COMMUNICATIONS. vol. 57, no. 6, June 1992, PRAGUE CS pages 1291 - 1298 FRANTISEK ADAMEK ET AL. 'Relative Reactivities of 1,1,1-Trichloroethane and 1,1,1-Trichlorotrifluoroethane in Competitive Addition Reactions' *
JOURNAL OF MOLECULAR CATALYSIS vol. 45, no. 2, 9 May 1988, LAUSANNE CH pages 169 - 174 DAVID M. GROVE ET AL. 'New Homogeneous Catalysts in the Addition of Polyhalogeno alkanes to Olefins; Organonickel(II)Com plexes [Ni(C6H3(CH2NMe2)2-o,o')XÜ (X=Cl,Br,I)' *

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