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WO2009067571A1 - Synthèse d'hydrofluoroalcanols et d'hydrofluoroalcènes - Google Patents

Synthèse d'hydrofluoroalcanols et d'hydrofluoroalcènes Download PDF

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Publication number
WO2009067571A1
WO2009067571A1 PCT/US2008/084107 US2008084107W WO2009067571A1 WO 2009067571 A1 WO2009067571 A1 WO 2009067571A1 US 2008084107 W US2008084107 W US 2008084107W WO 2009067571 A1 WO2009067571 A1 WO 2009067571A1
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Prior art keywords
group
metal
reactive metal
anhydride
reaction
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PCT/US2008/084107
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English (en)
Inventor
Mario Joseph Nappa
Xuehui Sun
Lev Moiseevich Yagupolskii
Andrey Anatolievich Filatov
Vladimir Nikolaevich Boiko
Yurii Lvovich Yagupolskii
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E. I. Du Pont De Nemours And Company
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Priority to EP08851477A priority Critical patent/EP2215097A1/fr
Priority to JP2010535049A priority patent/JP2011522772A/ja
Priority to CN2008801165517A priority patent/CN101861322B/zh
Priority to BRPI0818958A priority patent/BRPI0818958A2/pt
Publication of WO2009067571A1 publication Critical patent/WO2009067571A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F3/00—Compounds containing elements of Groups 2 or 12 of the Periodic Table
    • C07F3/003—Compounds containing elements of Groups 2 or 12 of the Periodic Table without C-Metal linkages
    • 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
    • C07C17/10—Preparation of halogenated hydrocarbons by replacement by halogens of hydrogen atoms
    • 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
    • C07C23/00—Compounds containing at least one halogen atom bound to a ring other than a six-membered aromatic ring
    • C07C23/02—Monocyclic halogenated hydrocarbons
    • C07C23/06—Monocyclic halogenated hydrocarbons with a four-membered ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/36—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions with formation of hydroxy groups, which may occur via intermediates being derivatives of hydroxy, e.g. O-metal
    • C07C29/38—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions with formation of hydroxy groups, which may occur via intermediates being derivatives of hydroxy, e.g. O-metal by reaction with aldehydes or ketones
    • C07C29/40—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions with formation of hydroxy groups, which may occur via intermediates being derivatives of hydroxy, e.g. O-metal by reaction with aldehydes or ketones with compounds containing carbon-to-metal bonds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/62—Halogen-containing esters
    • C07C69/63—Halogen-containing esters of saturated acids
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/04—Systems containing only non-condensed rings with a four-membered ring

Definitions

  • This disclosure relates in general to a process for the production of hydrofluoroalkanols, and a process for the production of hydrofluoroalkenes, and in particular a process for the production of 2,3,3,3-tetrafluoro-1 -propene, from hydrofluoroalkanols and hydrofluoroalkanol esters.
  • the present invention provides for the manufacture of hydrofluoroalkanols and hydrofluoroalkenes. Described herein is a process for the manufacture of hydrofluoroalkanols of the structure R f CFXCHROH, comprising reacting a halofluorocarbon of the structure RfCFX 2 , wherein each X is independently selected from Cl, Br, and I, with an aldehyde and a reactive metal in a reaction solvent to generate a reaction product comprising a metal hydrofluoroalkoxide, neutralizing said the metal hydrofluoroalkoxide to produce a hydrofluoroalkanol, and, optionally, recovering the hydrofluoroalkanol.
  • the reductive dehydroxyhalogenation comprises reacting the metal hydrofluoroalkoxide with a carboxylic acid anhydride and a reactive metal to form the hydrofluoroalkene.
  • the reductive dehydroxyhalogenation comprises neutralizing the metal hydrofluoroalkoxide to produce a hydrofluoroalkanol, mixing a dehydrating agent with said hydrofluoroalkanol thereby forming a gaseous mixture, and contacting a catalyst with said gaseous mixture, thereby forming the hydrofluoroalkene.
  • the methods comprise the steps of manufacturing hydrofluoroalkenes as described above, wherein R f is CF 3 .
  • Also disclosed is a method for the manufacture of hydrofluoroalkenes of the structure RfCF CHR, comprising reacting a hydrofluoroalkanol of structure RfCFXCHROH or a hydrofluoroalkoxide of structure RfCFXCHROMX, wherein M is a reactive metal in the +2 oxidation state and wherein X is selected from Cl, Br, and I, with a carboxylic acid anhydride and a reactive metal in a reaction solvent to form a hydrofluoroalkene, and isolating the hydrofluoroalkene.
  • R f is a perfluoroalkyl group having from one to four carbon atoms
  • X is selected from Cl, Br, and I
  • R is CH 3 , CH 3 CH 2 , CH 3 CH 2 CH 21 (CHs) 2 CH Or H.
  • reactive metal refers to reactive metals such as magnesium turnings, activated zinc powder, aluminum, and a powder of any of the following metals: magnesium, calcium, titanium, iron, cobalt, nickel, copper, zinc and indium, and also zinc(ll) salts.
  • Magnesium turnings are pieces of magnesium which are cut to produce small pieces with higher surface areas and generally low amounts of surface oxides (which reduce reactivity).
  • the reactive metal powders of magnesium, calcium, titanium, iron, cobalt, nickel, copper, zinc and indium are Rieke metals, which are prepared by a specific procedure which produces high surface area metal powders which are very reactive in reactions such as those of the present invention. Without wishing to be bound by any particular theory, Rieke metals are thought to be highly reactive because they have high surface areas and lack passivating surface oxides.
  • a dehydrating agent is a gas or gaseous mixture containing at least one gas selected from the group consisting of: methane, ethane, propane, butane, natural gas, alcohols, aldehydes, and carbon monoxide.
  • natural gas refers to a gaseous mixture having methane as the major component, but also comprising quantities of ethane, butane, propane, carbon dioxide, nitrogen.
  • dehydroxyhalogenating refers to removing a hydroxyl group and a halogen atom, chosen from Cl, Br and I, from adjacent carbon atoms of a hydrofluoroalkanol to form a hydrofluoroalkene.
  • hydrofluoroalkanols of the formula RfCFXCHROH such as 1 ,1 ,1 ,2-tetrafluoro-2-chloropropanol, an intermediate that may be converted into 2,3,3,3-tetrafluoro-1 -propene (HFC-1234yf), are prepared.
  • R is selected from the group consisting of CH 3 , CH 3 CH 2 , CH 3 CH 2 CH 2 , (CH 3 ) 2 CH or H.
  • R f is a perfluoroalkyl group having from one to four carbon atoms.
  • R f is selected from the group consisting of perfluoromethyl, perfluoroethyl, perfluoro-n-propyl, perfluoro-i-propyl, perfluoro-n-butyl and perfluoro-i-butyl, respectively, i.e., CF 3 -, CF 3 CF 2 -, CF 3 CF 2 CF 2 -, (CFs) 2 CF-, CF 3 CF 2 CF 2 - and CF 3 CF(CF 3 )CF 2 -, respectively.
  • R f is CF 3 and R is H.
  • X is selected from Cl, Br, and I. In another embodiment, X is Cl.
  • halofluorocarbons of the formula RfCFX 2 wherein each X is independently selected from Cl, Br, and I, are reacted with an aldehyde, and a reactive metal in a reaction solvent to generate a metal hydrofluoroalkoxide.
  • the metal hydrofluoroalkoxide is neutralized to provide a hydrofluoroalkanol, which can be isolated.
  • the neutralization comprises dilution with an organic solvent, and reaction with a dilute aqueous solution of an acid, including without limitation dilute aqueous hydrochloric acid or dilute aqueous sulfuric acid.
  • the organic solvent phase is washed further with an aqueous salt solution.
  • the organic solvent phase is then dried and the solvent removed by evaporation or distillation to provide the hydrofluoroalkanol product.
  • the metal hydrofluoroalkoxide may be used in further reactions as described later to produce a hydrofluoroalkene without neutralization.
  • the halofluorocarbon is 1 ,1 ,dichlorotetrafluoroethane and the hydrofluoroalkanol is 2-chloro- 2,3,3,3-tetrafluoro-1 -propanol.
  • Halofluorocarbons of the formula RfCFX 2 wherein each X is independently selected from Cl, Br, and I may be prepared by halogenation of the corresponding hydrofluorocarbons R f CFH 2 .
  • Rf is CF 3 and X is Cl
  • 1 ,1 ,1 ,2- tetrafluoroethane (HFC-134a) is chlorinated to prepare 1 ,1 ,1 ,2-tetrafluoro- 2,2-dichloroethane (CFC-114a).
  • a zinc salt is added to the mixture comprising the reaction of the halofluorocarbon.
  • Suitable zinc salts include zinc acetate, zinc bromide, zinc chloride, zinc citrate, zinc sulfate and mixtures thereof.
  • the zinc salt is zinc acetate.
  • the amount of zinc salt added is from 0.1 to 1.0 mole per mole of halofluorocarbon.
  • the amount of zinc salt added is from 0.25 to 0.7 mole per mole of halofluorocarbon.
  • the amount of zinc salt added is from 0. 5 to 0.6 mole per mole of halofluorocarbon.
  • the aldehyde is selected from the group consisting of formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde and isobutyraldehyde.
  • the mole ratio of reactive metal to halofluorocarbon is about 1 :1. In another embodiment, the mole ratio of reactive metal to halofluorocarbon is about 2:1. In yet another embodiment, the mole ratio of reactive metal to halofluorocarbon is about 2.5:1. In one embodiment, the mole ratio of aldehyde to halofluorocarbon is about 1 :1. In another embodiment, the mole ratio of aldehyde to halofluorocarbon is about 2:1.
  • the mole ratio of aldehyde to halofluorocarbon is about 3:1.
  • a quaternary ammonium salt is added to the reaction.
  • the quaternary ammonium salt is a bis-alkyldimethyl ammonium acetate. Without wishing to be bound by any particular theory, such quaternary ammonium salts are believed to promote the decomposition of paraformaldehyde to formaldehyde.
  • the amount of quaternary ammonium salt added is from about 1 % to about 20% by weight of the amount of paraformaldehyde. In other embodiments, the amount of quaternary ammonium salt added is from about 5% to about 10% by weight of the amount of paraformaldehyde.
  • reaction solvent is selected from the group consisting of alkyl, dialkyl, and trialkyl linear or cylic amines, N-methylpyrrolidine, N-methylpipehdine, sulfoxides, ethers, pyridine or alkyl-substituted pyridines, pyrazine or pyhmidine, alkyl and aromatic nitriles, hexamethylphosphoramide, alcohols, esters, and mixtures thereof.
  • an alcohol solvent is methanol.
  • an ester solvent is methyl formate.
  • a sulfoxide solvent is dimethylsulfoxide.
  • an alkyl nitrile solvent is acetonitrile.
  • an aromatic nitrile solvent is benzonitrile.
  • the reaction solvent is selected from the group consisting of trialkylamines, N-methylpyrrolidine, N-methylpiperidine, pyridine, alkyl-substituted pyridines, dimethylformamide, pyrazine or pyrimidine, and mixtures thereof.
  • the reaction solvent is selected from the group consisting of dimethylformamide, tetrahydrofuran, pyridine, dimethylacetamide, 1 ,4-dioxane, N-methyl pyrrolidone, diethyl ether, and mixtures thereof.
  • the reaction solvent is pyridine or alkyl-substituted pyridines, or mixtures thereof.
  • the reaction solvent is a mixture of pyridine or alkyl- substituted pyridines, and dimethylformamide.
  • the amount of water present in the reaction of the halofluorocarbon with an aldehyde and reactive metal is less than 1000 ppm. In another embodiment, the amount of water present in the reaction of the halofluorocarbon with an aldehyde and reactive metal is about 500 ppm. In yet another embodiment, the amount of water present in the reaction of the halofluorocarbon with an aldehyde and reactive metal is from about 100 to about 300 ppm. In one embodiment, the reaction of the halofluorocarbon with an aldehyde and reactive metal is performed at a temperature of from about 30 0 C to about 100 0 C.
  • the reaction of the halofluorocarbon with an aldehyde and reactive metal is performed at a temperature of from about 50°C to about 80°C. In one embodiment, the reaction is conducted for from about 3 to about 10 hours. In another embodiment, the reaction of the halofluorocarbon with an aldehyde and reactive metal is conducted for from about 4 to about 8 hours. In yet another embodiment, the reaction of the halofluorocarbon with an aldehyde and reactive metal is conducted for from about 4 to about 6 hours.
  • the aldehyde is pre-treated with the reaction solvent for a period of time before the reaction.
  • paraformaldehyde is pre-treated in pyridine for four hours at 60 0 C prior to reaction with halofluorocarbon and reactive metal.
  • the pre-treatment occurs for two hours.
  • the pre- treatment occurs for six hours.
  • there is no pre- treatment and the reaction is commenced upon charging all of the reactants and reaction solvent to the reaction vessel sequentially.
  • the reaction of the halofluorocarbon with an aldehyde and reactive metal is performed in a closed vessel or other reactor.
  • reaction of the halofluorocarbon with an aldehyde and reactive metal is performed under autogenous pressure.
  • the reaction of the halofluorocarbon with an aldehyde and reactive metal is performed in an open vessel or reactor, equipped with a suitable condenser to prevent escape of unreacted halofluorocarbon.
  • R f is a perfluoroalkyl group having from one to four carbon atoms.
  • R f is CF 3 and R is H.
  • the process for producing a hydrofluoroalkene comprises neutralizing the reaction product to produce a hydrofluoroalkanol; mixing a dehydrating agent with the hydrofluoroalkanol, thereby forming a gaseous mixture; and contacting a catalyst with the gaseous mixture, thereby forming the hydrofluoroalkene .
  • the reaction product of a chlorofluoroalkane, an aldehyde and a reactive metal is neutralized by diluting the reaction product mixture with a mixture of a solvent, ice, and an aqueous solution of an acid.
  • the solvent can be any commonly used organic solvent, such as diethyl ether.
  • the aqueous solution of an acid is an aqueous solution of a common mineral acid, such as hydrochloric acid.
  • the layer comprising the organic solvent is separated.
  • the organic solvent layer can be subsequently washed with a dilute aqueous solution of an acid, followed by a brine solution.
  • the organic layer is then dried.
  • the drying is accomplished by stirring the organic layer over and anhydrous salt, such as anhydrous magnesium sulfate or anhydrous sodium sulfate.
  • the organic solvent can then be evaporated to afford the hydrofluoroalkanol.
  • the hydrofluoroalkanol is at least one selected from the group consisting of: fluoroalkanols having the general formula R f 'CH2OH wherein R f ' is selected from the group consisting of: CF 3 CFCI-, CF 3 CF 2 CFCI-, CF 3 CF 2 CF 2 CFCI- and CF 3 CF 2 CF 2 CFCI-.
  • the hydrofluoroalkanol is 2,3,3,3-tetrafluoro-2-chloro-1 - propanol.
  • the catalyst is at least one transition metal.
  • the metal is selected from the group consisting of: nickel (Ni), palladium (Pd), and platinum (Pt).
  • the catalyst is a supported catalyst which comprises a transition metal and a support material.
  • the support material is at least one selected from the group consisting of activated carbon and /-alumina.
  • the dehydrating agent is at least one gas selected from the group consisting of: methane, ethane, propane, butane, natural gas, alcohols, aldehydes, and carbon monoxide.
  • the mixing step takes place at a temperature in the range between about 65-80 0 C.
  • the process further comprises preheating the gaseous mixture prior to the contacting step.
  • the preheating takes place at a temperature in the range between about 250 to about 450 0 C.
  • the contacting step preferably takes place at a temperature in the range between about 400 to about 700°C.
  • the contacting step also preferably takes place for between about 20 to about 25 seconds.
  • the process further comprises the step of neutralizing any residual HF contained in the hydrofluoroalkene product, wherein the HF is neutralized by passing the hydrofluoroalkene product through a KOH solution.
  • the gaseous mixture may further comprise at least one diluent inert gas selected from the group consisting of: nitrogen, helium, and argon.
  • the conversion of the hydrofluoroalkanol to hydrofluoroalkene is in the range between about 50 to about 100%.
  • the selectivity of hydrofluoroalkanol to hydrofluoroalkene is in the range between about 29 to about 100%.
  • the pressure during the contacting step is in the range between about 1 to about 100 psig.
  • the reductive dehydroxyhalogenation comprises reacting the metal hydrofluoroalkoxide with a carboxylic acid anhydride and a reactive metal.
  • the hydrofluoroalkanol of structure RfCFXCHROH or a hydrofluoroalkoxide of structure R f CFXCHROMX, wherein M is a reactive metal in the +2 oxidation state react first with the carboxylic acid anhydride to form an ester as described below. This ester then reacts with the reactive metal to form a hydrofluoroalkene.
  • R f is selected from the group consisting of perfluoromethyl, perfluoroethyl, perfluoro-n-propyl, perfluoro-i-propyl, perfluoro-n-butyl and perfluoro-i-butyl
  • X is selected from Cl, Br, and I
  • R is selected from the group consisting of H, CH 3 , C 2 H 5 , n-CsH / , and i- C 3 H 7 , and in particular R f is CF 3
  • X is Cl and R is H.
  • the carboxylic acid anhydride is selected from the group consisting of acetic anhydride, propionic anhydride, butyric anhydride, succinic anhydride, glutaric anhydride, adipic anhydride, and formic anhydride.
  • the reactive metal powder is as described above.
  • the reductive dehydroxyhalogenation can be done without neutralizing the product mixture from the reaction of a halofluorocarbon with a reactive metal and an aldehyde.
  • the reductive dehydroxyhalogenation is done after first isolating the hydrofluoroalkanol, and then reacting it with a carboxylic acid anhydride and a reactive metal.
  • the reductive dehydroxyhalogenation is done without isolating the ester. In other embodiments, the reductive dehydroxyhalogenation is done with the ester being isolated from the solvent and metal salts, and then reacted with the reactive metal.
  • the product of the reductive dehydroxyhalogenation further comprises a substituted cyclobutane of the formula cyclo-(-CF(R f )CHRCF(R f )CHR-), wherein R f is a perfluoroalkyl group having from one to four carbon atoms and R is CH 3 , CH 3 CH 2 , CH 3 CH 2 CH 2 , (CH 3 ) 2 CH or H. In one particular embodiment, R f is CF 3 and R is H.
  • the carboxylic acid anhydride is selected from the group consisting of acetic anhydride, propionic anhydride, butyric anhydride, succinic anhydride, glutaric anhydride, adipic anhydride, and formic anhydride.
  • the carboxylic acid anhydride is acetic anhydride.
  • the mole ratio of carboxylic acid anhydride to hydrofluoroalkanol is from about 1 :1 to about 2:1.
  • the mole ratio of carboxylic acid anhydride to hydrofluoroalkanol is from about 1.4:1 to about 1.8:1.
  • the mole ratio of reactive metal to hydrofluoroalkanol is about 1 :1.
  • the mole ratio of reactive metal to hydrofluoroalkanol is about 2:1. In yet another embodiment, the mole ratio of reactive metal to hydrofluoroalkanol is about 2.5:1.
  • R f is CF 3
  • R is H
  • X is Cl
  • R' is CH 3 .
  • the reductive dehydroxyhalogenation is conducted in a reaction solvent which is the same solvent in which the reaction of a halofluorocarbon with reactive metal and an aldehyde is conducted in.
  • the reductive dehydroxyhalogenation is conducted in a reaction solvent which is a different solvent than the reaction of a halofluorocarbon with reactive metal and an aldehyde is conducted in.
  • the reductive dehydroxyhalogenation is conducted in a mixture of pyridine or an alkyl-substituted pyridine, and dimethylformamide.
  • the terms “comprises,” “comprising,” “includes,” “including,” “has,” “having” or any other variation thereof, are intended to cover a non-exclusive inclusion.
  • a process, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.
  • “or” refers to an inclusive or and not to an exclusive or. For example, a condition A or B is satisfied by any one of the following: A is true (or present) and B is false (or not present), A is false (or not present) and B is true (or present), and both A and B are true (or present).
  • Example 1 demonstrates the preparation of 2-chloro-3,3,3- trifluoropropanol from 1 ,1 ,1 ,2-tetrafluoro-2,2-dichloroethane.
  • Example 2 demonstrates the conversion of 2-chloro-2, 3,3,3- tetrafluoropropanol to 2,3,3,3- tetrafluoroi -propene.
  • Example 3 demonstrates the synthesis of 2,3,3,3- tetrafluoro-1 - propene from 1 ,1 ,1 ,2-tetrafluoro-2,2-dichloroethane.
  • a 400 ml Hastelloy C shaker tube was charged with 20 g (0.315 mol) of activated Zinc powder, 7.5g (0.25 mol) of paraformaldehyde and 130 ml anhydrous DMF under N 2 . The tube was cooled down to -15 0 C and 43 g (0.25 mol) of 1 ,1 -dichlorotetrafluoroethane were added. Then the reaction mixture was stirred at 60 0 C for 6 hours.
  • Example 4 demonstrates the synthesis of 2-chloro-2, 3,3,3- tetrafluoropropanol (CF 3 CCIFCH 2 OH) in pyridine.
  • Example 5 demonstrates the synthesis of 2-chloro-2, 3,3,3- tetrafluoropropanol CF 3 CCIFCH 2 OH in dimethylacetamide.
  • Example 6 demonstrates the synthesis of 2-chloro-2, 3,3,3- tetrafluoropropanol CF 3 CCIFCH 2 OH in pyridine, with pre-treatment of formaldehyde.
  • a 80 ml Fisher Porter tube was charged with 1.82g (0.06 mol) of paraformaldehyde and 30 ml anhydrous pyridine under N 2 .
  • the tube was heated up to 60 0 C and stirred at 60 0 C for 4hr. Then it was cooled down to room temp and 2.24 g (0.034 mol) of activated Zinc powder were added. After purging with N 2 for 15 min, the tube was cooled down to -15 0C and 5 g (0.029 mol) of 1 ,1 -dichlorotetrafluoroethane were added.
  • CF 3 CCIFCH 2 OZnCI (analyzed as CF 3 CCIFCH 2 OH) increased to 78.7%.
  • Example 7 illustrates the esterification of 2,3,3, 3-tetrafluoro-2- chloropropanol with acetic anhydride to produce 2,3,3,3-tetrafluoro-2- chloropropyl acetate.
  • Example 8 illustrates the direct esterification of CF 3 CCIFCH 2 OZnCI to CF 3 CCIFCH 2 OAC. 10 ml of a pyridine solution containing about 14%
  • CF 3 CCIFCH 2 OZnCI was vacuum evaporated at room temp to remove the majority of the pyridine. Then 2.Og acetic anhydride and 1 ml DMF were added into the resultant solid. The mixture was stirred at 60 0 C for 7hr.
  • Example 9 illustrates the conversion of CF 3 CCIFCH 2 OAC to 2,3,3,3- tetrafluoropropene.
  • Example 10 demonstrates the reaction of 1 ,1 - dichlorotetrafluoroethane with paraformaldehyde in a mixed solvent of dimethylformamide and pyridine to produce CF 3 CCIFCH 2 OZnCI.
  • a 80 ml Fisher Porter tube was charged with 2.2g Zn (0.037 mol), 0.3g Zinc acetate (0.0016mol), 2g (0.067 mol) of paraformaldehyde, 15g of anhydrous pyridine and 15g of dimethylformamide under N 2 . After N 2 purge for 15 min, the tube was cooled down to -15 0 C and 5 g (0.029 mol) of 1 ,1 -dichlorotetrafluoroethane were added. Then the reaction mixture was stirred at 50 0 C for 2 hours. The pressure of the reactor dropped to 5 psig at end of reaction from 25 psig. After the reaction mixture cooled down to room temperature, it was analyzed by GC-MS.
  • Example 11 illustrates esterification of CF 3 CCIFCH 2 OZnCI directly to CF 3 CCIFCH 2 OAC with acetic anhydride in a solvent mixture.
  • Example 12 illustrates the synthesis of 2,3,3,3- tetrafluoroi -propene from 1 ,1 ,1 ,2-tetrafluoro-2,2-dichloroethane in 3:1 pyridine:DMF solvent.
  • Solvent pyridine was excluded from integration. The data is reported in Table 11 by area percent of GC-MS. The selectivity of 1 ,1 -dichlorotetrafluoroethane to CF 3 CCIFCH 2 OZnCI (analyzed as CF 3 CCIFCH 2 OH) is 81 % based on GC-MS analysis.
  • Example 13 illustrates the synthesis of 2,3,3,3- tetrafluoro-1- propene from 1 ,1 ,1 ,2-tetrafluoro-2,2-dichloroethane in 1 :1 pyridine:DMF solvent.
  • a 80 ml Fisher Porter tube was charged with 2.1 g Zn (0.032), 0.3g
  • the reaction mix above was treated with 2g Na 2 CO 3 in 80 ml Fisher Porter tube. After Na 2 CO 3 was filtrated off, activated Zinc powder (1g, 0.015mol) was added. The reaction was run in an 80ml Fisher Porter tube at 60 0 C for 4hr with stirring. The pressure of the reactor increased from 5 psig to 18 psig. After the reaction mixture cooled down to room temperature, it was analyzed by GC-MS. The data is reported by area percent of GC-MS. The result of vapor phase was listed in Table 17 and the result of liquid phase was reported in Table 18 (solvent DMF and pyridine was excluded from integration).
  • Example 14 illustrates the synthesis of 2,3,3,4,4,4- hexafluoro-1 - butene from 1 ,1 ,1 ,2,2,3-hexafluoro-3,3-dichloropropane in 1 :1 pyhdine:DMF solvent.
  • a 80 ml Fisher Porter tube is charged with 2.1 g Zn (0.032), 0.3g Zinc acetate (0.0016mol), 2g (0.067 mol) of paraformaldehyde, 0.2g Bis(hydrogenated alkyl) dimethyl ammonium acetate and 3Og anhydrous pyridine under N 2 . After purging with N 2 for 15 min, the tube is cooled down to -15 0 C and 6.4 g (0.029 mol) of 1 ,1 ,1 , 2,2,3-hexafluoro-3,3- dichloropropane was added. Then the reaction mixture is stirred at 50 0 C for 3 hours. The pressure of the reactor drops to 5.5 psig at end of reaction from 23 psig.
  • reaction mixture After the reaction mixture cooled down to room temperature, it is analyzed by GC-MS.
  • GC-MS analysis a portion of the reaction mixture is acidified with a 10% solution of HCI in acetone. Solvents DMF and pyridine are excluded from integration. The data is reported in Table 18 by area percent of GC-MS.
  • the selectivity of 216cb to CF 3 CF 2 CCIFCH 2 OZnCI (analyzed as CF 3 CF 2 CCIFCH 2 OH) is about 85% based on GC-MS analysis.
  • the reaction mix above is then treated with 2g Na 2 CO 3 in an 80 ml Fisher Porter tube. After Na 2 CO 3 is filtrated off, activated Zinc powder (1g, 0.015mol) is added. The reaction is run in an 80ml Fisher Porter tube at 60 0 C for 4hr with stirring. The pressure of the reactor increases from 5 psig to 18 psig. After the reaction mixture is cooled down to room temperature, it is analyzed by GC-MS. The data is reported by area percent of GC-MS. The result of vapor phase is listed in Table 20 and the result of liquid phase is reported in Table 21 (solvent DMF and pyridine was excluded from integration).

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Abstract

L'invention concerne un procédé de fabrication d'hydrofluoroalcanols de la structure RfCFClCHROH, comprenant la réaction d'un halogénofluorocarbone de la structure RfCFX2, chaque X étant indépendamment sélectionné parmi Cl, Br, et I, avec un aldéhyde et un métal réactif dans un solvant de réaction pour générer un produit de réaction comprenant un hydrofluoroalcoxyde métallique, la neutralisation de l'hydrofluoroalcoxyde métallique pour produire un hydrofluoroalcanol, et la récupération de l'hydrofluoroalcanol. Des procédés de fabrication d'hydrofluoroalcènes de la structure RfCF=CHR à partir d'halogénofluorocarbones de la structure RfCFX2 sont également décrits ci-dessus, chaque X étant indépendamment sélectionné parmi Cl, Br, et I, comprenant (1) la réaction des halogénofluorocarbones de la structure RfCFX2, chaque X étant indépendamment sélectionné parmi Cl, Br, et I, avec un aldéhyde et un métal réactif pour générer un produit de réaction comprenant un hydrofluoroalcoxyde métallique, et la déshydroxyhalogénation de manière réductrice de l'hydrofluoroalcoxyde métallique pour produire un hydrofluoroalcène ou (2) la réaction d'un hydrofluoroalcanol de la structure RfCFXCHROH ou d'un hydrofluoroalcoxyde de la structure RfCFXCHROMX, M étant un métal réactif dans l'étape d'oxydation +2, avec un anhydride d'acide carboxylique et un métal réactif dans un solvant de réaction pour former un hydrofluoroalcène, et l'isolation de l'hydrofluoroalcène. En particulier, un 2,3,3,3-tétrafluoro-1-propène peut être fabriqué avec ce procédé. Des composés de la formule RfCFClCHROC(=O)R' sont également décrits.
PCT/US2008/084107 2007-11-20 2008-11-20 Synthèse d'hydrofluoroalcanols et d'hydrofluoroalcènes WO2009067571A1 (fr)

Priority Applications (4)

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EP08851477A EP2215097A1 (fr) 2007-11-20 2008-11-20 Synthèse d'hydrofluoroalcanols et d'hydrofluoroalcènes
JP2010535049A JP2011522772A (ja) 2007-11-20 2008-11-20 ヒドロフルオロアルカノールおよびヒドロフルオロアルケンの合成
CN2008801165517A CN101861322B (zh) 2007-11-20 2008-11-20 氢氟链烷醇和氢氟烯烃的合成
BRPI0818958A BRPI0818958A2 (pt) 2007-11-20 2008-11-20 "processos para a fabricação dos hidrofluoroalquenos, para a fabricação dos hidrofluoroalcanóis, para a fabricação dos hidrofluoroésteres e composto"

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UAA200712916 2007-11-20
UA2007012916 2007-11-20
US10433408P 2008-10-10 2008-10-10
UAA200812034 2008-10-10
UA2008012034 2008-10-10
US61/104,334 2008-10-10

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KR (1) KR20100099182A (fr)
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WO (1) WO2009067571A1 (fr)

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WO2010042781A2 (fr) * 2008-10-10 2010-04-15 E. I. Du Pont De Nemours And Company Compositions comprenant du 2,3,3,3-tétrafluoropropène, du 2-chloro-2,3,3,3-tétrafluoropropanol, de l'acétate de 2-chloro-2,3,3,3-tétrafluoropropyle ou du chlorure de (2-chloro-2,3,3,3-tétrafluoropropoxy)-zinc
US8258353B2 (en) 2008-10-13 2012-09-04 Dow Global Technologies, Llc Process for the production of chlorinated and/or fluorinated propenes
CN102791660A (zh) * 2009-12-29 2012-11-21 纳幕尔杜邦公司 由氟化醇合成氟化烯烃
US8558041B2 (en) 2009-10-09 2013-10-15 Dow Global Technologies, Llc Isothermal multitube reactors and processes incorporating the same
US8581012B2 (en) 2009-10-09 2013-11-12 Dow Global Technologies, Llc Processes for the production of chlorinated and/or fluorinated propenes and higher alkenes
US8581011B2 (en) 2009-10-09 2013-11-12 Dow Global Technologies, Llc Process for the production of chlorinated and/or fluorinated propenes
US8907148B2 (en) 2011-08-07 2014-12-09 Dow Global Technologies Llc Process for the production of chlorinated propenes
US8907149B2 (en) 2011-05-31 2014-12-09 Dow Global Technologies Llc Process for the production of chlorinated propenes
US8927792B2 (en) 2011-06-08 2015-01-06 Dow Agrosciences, Llc Process for the production of chlorinated and/or fluorinated propenes
US9056808B2 (en) 2011-05-31 2015-06-16 Dow Global Technologies, Llc Process for the production of chlorinated propenes
US9067855B2 (en) 2011-11-21 2015-06-30 Dow Global Technologies Llc Process for the production of chlorinated alkanes
US9169177B2 (en) 2011-12-22 2015-10-27 Blue Cube Ip Llc Process for the production of tetrachloromethane
US9199899B2 (en) 2011-12-02 2015-12-01 Blue Cube Ip Llc Process for the production of chlorinated alkanes
US9233896B2 (en) 2011-08-07 2016-01-12 Blue Cube Ip Llc Process for the production of chlorinated propenes
US9284239B2 (en) 2011-12-02 2016-03-15 Blue Cube Ip Llc Process for the production of chlorinated alkanes
US9321707B2 (en) 2012-09-20 2016-04-26 Blue Cube Ip Llc Process for the production of chlorinated propenes
US9334205B2 (en) 2011-12-13 2016-05-10 Blue Cube Ip Llc Process for the production of chlorinated propanes and propenes
US9382176B2 (en) 2013-02-27 2016-07-05 Blue Cube Ip Llc Process for the production of chlorinated propenes
US9403741B2 (en) 2013-03-09 2016-08-02 Blue Cube Ip Llc Process for the production of chlorinated alkanes
US9475740B2 (en) 2012-12-19 2016-10-25 Blue Cube Ip Llc Process for the production of chlorinated propenes
US9512053B2 (en) 2012-12-18 2016-12-06 Blue Cube Ip Llc Process for the production of chlorinated propenes
US9512049B2 (en) 2011-12-23 2016-12-06 Dow Global Technologies Llc Process for the production of alkenes and/or aromatic compounds
US9598334B2 (en) 2012-09-20 2017-03-21 Blue Cube Ip Llc Process for the production of chlorinated propenes
US9795941B2 (en) 2012-09-30 2017-10-24 Blue Cube Ip Llc Weir quench and processes incorporating the same
US10065157B2 (en) 2012-10-26 2018-09-04 Blue Cube Ip Llc Mixer and processes incorporating the same
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Cited By (32)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2010042781A3 (fr) * 2008-10-10 2010-07-08 E. I. Du Pont De Nemours And Company Compositions comprenant du 2,3,3,3-tétrafluoropropène, du 2-chloro-2,3,3,3-tétrafluoropropanol, de l'acétate de 2-chloro-2,3,3,3-tétrafluoropropyle ou du chlorure de (2-chloro-2,3,3,3-tétrafluoropropoxy)-zinc
US8147710B2 (en) 2008-10-10 2012-04-03 E. I. Du Pont De Nemours And Company Compositions comprising 2,3,3,3-tetrafluoropropene, 2-chloro-2,3,3,3-tetrafluoropropanol, 2-chloro-2,3,3,3-tetrafluoro-propyl acetate or zinc (2-chloro-2,3,3,3-tetrafluoropropoxy) chloride
US8518294B2 (en) 2008-10-10 2013-08-27 E I Du Pont De Nemours And Company Compositions comprising 2,3,3,3-tetrafluoropropene, 2-chloro-2,3,3,3-tetrafluoropropanol, 2-chloro-2,3,3,3-tetrafluoro-propyl acetate or zinc (2-chloro-2,3,3,3-tetrafluoropropdxy) chloride
WO2010042781A2 (fr) * 2008-10-10 2010-04-15 E. I. Du Pont De Nemours And Company Compositions comprenant du 2,3,3,3-tétrafluoropropène, du 2-chloro-2,3,3,3-tétrafluoropropanol, de l'acétate de 2-chloro-2,3,3,3-tétrafluoropropyle ou du chlorure de (2-chloro-2,3,3,3-tétrafluoropropoxy)-zinc
US8258353B2 (en) 2008-10-13 2012-09-04 Dow Global Technologies, Llc Process for the production of chlorinated and/or fluorinated propenes
US8933280B2 (en) 2009-10-09 2015-01-13 Dow Global Technologies Llc Processes for the production of hydrofluoroolefins
US8558041B2 (en) 2009-10-09 2013-10-15 Dow Global Technologies, Llc Isothermal multitube reactors and processes incorporating the same
US8581012B2 (en) 2009-10-09 2013-11-12 Dow Global Technologies, Llc Processes for the production of chlorinated and/or fluorinated propenes and higher alkenes
US8581011B2 (en) 2009-10-09 2013-11-12 Dow Global Technologies, Llc Process for the production of chlorinated and/or fluorinated propenes
US8926918B2 (en) 2009-10-09 2015-01-06 Dow Global Technologies Llc Isothermal multitube reactors
CN102791660A (zh) * 2009-12-29 2012-11-21 纳幕尔杜邦公司 由氟化醇合成氟化烯烃
US10407603B2 (en) 2010-11-25 2019-09-10 Arkema France Compositions of chloro-trifluoropropene and hexafluorobutene
US8907149B2 (en) 2011-05-31 2014-12-09 Dow Global Technologies Llc Process for the production of chlorinated propenes
US9056808B2 (en) 2011-05-31 2015-06-16 Dow Global Technologies, Llc Process for the production of chlorinated propenes
US8927792B2 (en) 2011-06-08 2015-01-06 Dow Agrosciences, Llc Process for the production of chlorinated and/or fluorinated propenes
US9475739B2 (en) 2011-08-07 2016-10-25 Blue Cube Ip Llc Process for the production of chlorinated propenes
US9233896B2 (en) 2011-08-07 2016-01-12 Blue Cube Ip Llc Process for the production of chlorinated propenes
US8907148B2 (en) 2011-08-07 2014-12-09 Dow Global Technologies Llc Process for the production of chlorinated propenes
US9067855B2 (en) 2011-11-21 2015-06-30 Dow Global Technologies Llc Process for the production of chlorinated alkanes
US9199899B2 (en) 2011-12-02 2015-12-01 Blue Cube Ip Llc Process for the production of chlorinated alkanes
US9284239B2 (en) 2011-12-02 2016-03-15 Blue Cube Ip Llc Process for the production of chlorinated alkanes
US9334205B2 (en) 2011-12-13 2016-05-10 Blue Cube Ip Llc Process for the production of chlorinated propanes and propenes
US9169177B2 (en) 2011-12-22 2015-10-27 Blue Cube Ip Llc Process for the production of tetrachloromethane
US9512049B2 (en) 2011-12-23 2016-12-06 Dow Global Technologies Llc Process for the production of alkenes and/or aromatic compounds
US9598334B2 (en) 2012-09-20 2017-03-21 Blue Cube Ip Llc Process for the production of chlorinated propenes
US9321707B2 (en) 2012-09-20 2016-04-26 Blue Cube Ip Llc Process for the production of chlorinated propenes
US9795941B2 (en) 2012-09-30 2017-10-24 Blue Cube Ip Llc Weir quench and processes incorporating the same
US10065157B2 (en) 2012-10-26 2018-09-04 Blue Cube Ip Llc Mixer and processes incorporating the same
US9512053B2 (en) 2012-12-18 2016-12-06 Blue Cube Ip Llc Process for the production of chlorinated propenes
US9475740B2 (en) 2012-12-19 2016-10-25 Blue Cube Ip Llc Process for the production of chlorinated propenes
US9382176B2 (en) 2013-02-27 2016-07-05 Blue Cube Ip Llc Process for the production of chlorinated propenes
US9403741B2 (en) 2013-03-09 2016-08-02 Blue Cube Ip Llc Process for the production of chlorinated alkanes

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BRPI0818958A2 (pt) 2017-12-12
KR20100099182A (ko) 2010-09-10
EP2215097A1 (fr) 2010-08-11
CN101861322A (zh) 2010-10-13
CN101861322B (zh) 2013-08-07
RU2010125261A (ru) 2011-12-27

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