CN104684877A - Dehydrochlorination of chlorinated reactants to produce 1,1,1,4,4,4-hexafluoro-2-butyne - Google Patents
Dehydrochlorination of chlorinated reactants to produce 1,1,1,4,4,4-hexafluoro-2-butyne Download PDFInfo
- Publication number
- CN104684877A CN104684877A CN201380050238.9A CN201380050238A CN104684877A CN 104684877 A CN104684877 A CN 104684877A CN 201380050238 A CN201380050238 A CN 201380050238A CN 104684877 A CN104684877 A CN 104684877A
- Authority
- CN
- China
- Prior art keywords
- hexafluoro
- butyne
- quaternary ammonium
- ammonium salts
- aqueous solution
- 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.)
- Pending
Links
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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Disclosed is a process for producing hexafluoro-2-butyne comprising, reacting HCFC-336 with an aqueous solution of an alkali metal hydroxide in the presence of a quaternary alkylammonium salt which comprises at least one alkyl group of at least 8 carbons, and recovering the hexafluoro-2-butyne, wherein the conversion of dichloro-1,1,1,4,4,4-hexafluorobutane is at least 50% per hour. Also disclosed is a process for producing hexafluoro-2-butyne comprising, reacting HCFC-336 with an aqueous solution of an alkali metal hydroxide in the presence of a quaternary alkylammonium salt having alkyl groups of from four to ten carbon atoms, and mixtures thereof, and a non-ionic surfactant, and recovering the hexafluoro-2-butyne, and wherein the conversion of dichloro-1,1,1,4,4,4-hexafluorobutane to hexafluoro-2-butyne is at least 20% per hour.
Description
Background technology
Technical field
The disclosure relates generally to the method for synthesizing fluorinated olefin and fluoridizing alkynes.
the description of association area
Because Montreal Protocol progressively stops using Chlorofluorocarbons (CFCs) (CFC) and the Hydrochlorofluorocarbons (HCFC) of loss ozone, therefore in the past in decades, fluorocarbon industry is devoted to find alternative refrigerant always.The solution of many application is to be used as refrigeration agent, solvent, fire-fighting medium, whipping agent and propelling agent by the commercialization of hydrogen fluorohydrocarbon (HFC) compound.These novel cpds most widely used such as HFC refrigeration agent, HFC-134a and HFC-125 at present, and blowing agent H FC-134a and 245fa has zero ozone depletion potential, the impact that it eliminates by current regulation gradually due to Montreal Protocol therefore can not be subject to.
Except ozone depletion problem, Global warming is another environmental problem in these application numerous.Therefore, the composition not only meeting low-ozone loss standard but also there is low global warming up trend is needed.It is believed that some HF hydrocarbon meets this two targets.Therefore, need the preparation method providing halohydrocarbon and fluoroolefins, described halohydrocarbon and fluoroolefins do not comprise chlorine, simultaneously concrete low global warming up trend.Determine the multiple HF hydrocarbon meeting these targets.This type of alkene a kind of is 1,1, Isosorbide-5-Nitrae, 4,4-hexafluoro-2-butylene.Need the efficient synthesis of this compounds.
Summary of the invention
The invention discloses the method for the preparation of hexafluoro-2-butyne, described method comprises the reactant aqueous solution making chlorination reaction thing and alkali metal hydroxide in the presence of a phase transfer catalyst.In one embodiment, chlorination reaction thing comprises chlorine fluorine butane or chlorine fluorine butylene.In one embodiment, described chlorination reaction thing is IHCFC-336mdd (2,3-bis-chloro-1,1, Isosorbide-5-Nitrae, 4,4-hexafluoro butane), HCFC-336mfa (2,2-bis-chloro-1,1, Isosorbide-5-Nitrae, 4,4--hexafluoro butane) or HCFO-1326mxz (E-or Z-1,1,1, the chloro-2-butylene of 4,4,4-hexafluoro-2-).As used herein, HCFC-336 is intended to comprise any one or both in aforementioned HCFC-336 isomer.In one embodiment, phase-transfer catalyst is alkyl quaternary ammonium salts.In one embodiment, alkyl quaternary ammonium salts has at least one alkyl group, and described alkyl group has at least 8 carbon, and reclaims hexafluoro-2-butyne, wherein two chloro-1,1, and Isosorbide-5-Nitrae, the transformation efficiency of 4,4-hexafluoro butane is per hour at least 50%.
The invention also discloses a kind of method for the preparation of hexafluoro-2-butyne, described method comprises: have containing under the alkyl group of four to ten carbon atoms and the alkyl quaternary ammonium salts of their mixture and the existence of nonionogenic tenside, make the reactant aqueous solution of chlorination reaction thing and alkali metal hydroxide, and reclaim hexafluoro-2-butyne, and wherein chlorination reaction thing is per hour at least 20% to the transformation efficiency of hexafluoro-2-butyne.
More than summary and following embodiment are only exemplary with illustrative instead of restrictive to the present invention, and the present invention limits by claims.
Embodiment
The invention discloses a kind of method for the preparation of hexafluoro-2-butyne, described method comprises: under the existence of alkyl quaternary ammonium salts, makes the reactant aqueous solution of chlorination reaction thing and alkali metal hydroxide, and described alkyl quaternary ammonium salts comprises at least one alkyl group, described alkyl group has at least 8 carbon, and reclaim hexafluoro-2-butyne, wherein two chloro-1,1,1, the transformation efficiency of 4,4,4-hexafluoro butane is per hour at least 50%.
The invention also discloses a kind of method for the preparation of hexafluoro-2-butyne, described method comprises: have containing under the alkyl group of four to ten carbon atoms and the alkyl quaternary ammonium salts of their mixture and the existence of nonionogenic tenside, make the reactant aqueous solution of chlorination reaction thing and alkali metal hydroxide, and reclaim hexafluoro-2-butyne, and wherein chlorination reaction thing is per hour at least 20% to the transformation efficiency of hexafluoro-2-butyne.
Be described above many aspects and embodiment, and be only illustrative rather than restrictive.After reading this specification, technician it should be understood that without departing from the present invention, and other aspects and embodiment are also possible.
According to following embodiment and according to claim, other characteristic sum beneficial effects of any one or more embodiments will be apparent.In addition, although hereafter describing individually, stating or illustrating, each characteristic sum key element of embodiment disclosed herein can separately, be engaged with each other or combinationally use.
As used herein, the title HCFC-336 of specified location isomer does not refer to HCFC-336mdd (2,3-bis-chloro-1,1,1,4,4,4-hexafluoro butane) or HCFC-336mfa (2,2-bis-chloro-1,1, Isosorbide-5-Nitrae, 4,4-hexafluoro butane) in any one or both.As used herein, do not specify stereochemical title HCFC-1326mxz to refer to any one or both in E-or Z-HCFC-1326mxz (E-1,1, Isosorbide-5-Nitrae, the chloro-2-butylene of 4,4-hexafluoro-2-or Z-1,1, Isosorbide-5-Nitrae, the chloro-2-butylene of 4,4-hexafluoro-2-).
HCFC-336 obtains by number of ways is potential, and as 1,1, Isosorbide-5-Nitrae, the potential precursor of 4,4-hexafluoro-2-butylene and cause concern.The hydrogenation of HCFC-336 by CFC-1316mxx or the chlorination by HFC-356mff are prepared.Dehydrochlorination will provide hexafluoro-2-butyne twice, and it can be easy to be hydrogenated to provide cis-1,1,1,4,4,4-hexafluoro-2-butene.Although dehydrochlorination seems for the first time will be simple, the dehydrochlorination of vinylchlorid is the classical organic chemistry forming acetylene, and it requires suitable exacting terms, such as very strong alkali, as the liquid ammonia solution of sodium.Report and used alkali aqueous solution at the temperature of 100-120 DEG C to the highest 200 or 250 DEG C, the polyfluoro vinylchlorid dehydrohalogenation of higher molecular weight can have been become alkynes.But, at these tem-peratures, the vapour pressure that hexafluoro-2-butyne will have in too high reactor, and the impact being subject to degraded.
Find, alkali aqueous solution and the combination as the alkyl quaternary ammonium salts of phase-transfer catalyst can be used, at the temperature far below 100 DEG C, make HCFC-336mdd or HCFC-336mfa dehydrochlorination twice.
As used herein, phase-transfer catalyst is intended to represent and is conducive to ionic compound from aqueous phase or the material transferred to from solid phase organic phase.Described phase-transfer catalyst is conducive to the reaction of these different and incompatible components.Although different phase-transfer catalysts can act in a different manner, their mechanism of action does not determine their effectiveness in the present invention, and precondition is that described phase-transfer catalyst is conducive to dehydrochlorination reaction.
As used herein, phase-transfer catalyst is alkyl quaternary ammonium salts, and wherein said alkyl group is the alkyl chain with four to ten carbon atoms.In one embodiment, alkyl quaternary ammonium salts is methyl tricapryl ammonium chloride (Aliquat 336).The negatively charged ion of described salt can be that halogen ion is as chlorion or bromide anion, hydrogen sulfate ion or other conventional negatively charged ion any.
In another embodiment, alkyl quaternary ammonium salts is four octyl group ammonium chlorides.In another embodiment, alkyl quaternary ammonium salts is four octyl sulfate hydrogen ammoniums.
Usually be construed to other compound of phase-transfer catalyst in other applications, comprise crown ether, cave ether or independent nonionogenic tenside, not there is the remarkably influenced of transformation efficiency on the dehydrochlorination reaction of same way or speed.
In another embodiment, the combination of alkaline aqueous solution and alkyl quaternary ammonium salts can be used, and combination that is other and nonionogenic tenside, by HCFC-336mdd or HCFC-336mfa twice dehydrochlorination at the temperature far below 100 DEG C, wherein said alkyl group is the alkyl chain with an at least four or more carbon atom.An example of this type of alkyl quaternary ammonium salts is tetrabutylammonium chloride.
In one embodiment, nonionogenic tenside is ethoxylized nonylphenol class or ethoxylation C12-C15 straight-chain fatty alcohol.Suitable nonionogenic tenside comprises purchased from Stepan Company's
n25-9 and
10.
In one embodiment, alkyl quaternary ammonium salts is selected from tetrabutylammonium chloride, Tetrabutyl amonium bromide, 4-butyl ammonium hydrogen sulfate, four octyl group ammonium chlorides, four octyl group brometo de amonios, four octyl sulfate hydrogen ammoniums, methyl tricapryl ammonium chloride, methyl trioctylphosphine brometo de amonio, four decyl ammonium chlorides, four decyl brometo de amonios and four (12) alkyl ammomium chloride.
The dehydrochlorination Useful alkyls quaternary ammonium salt of HCFC-336 carries out, and wherein said alkyl group is alkyl chain, and described alkyl chain has the alkyl chain that at least one has 8 or more carbon.In another embodiment, described alkyl quaternary ammonium salts has the alkyl chain that three have 8 or more carbon, such as methyl trioctylphosphine ammonium salt.In another embodiment, alkyl quaternary ammonium salts is four octyl group ammonium salts.The negatively charged ion of described salt can be that halogen ion is as chlorion or bromide anion, hydrogen sulfate ion or other conventional negatively charged ion any.
In one embodiment, alkyl quaternary ammonium salts adds with the amount of 0.5 of HCFC-336 % by mole to 2.0 % by mole.In another embodiment, alkyl quaternary ammonium salts adds with the amount of 1 of HCFC-336 % by mole to 2 % by mole.In another embodiment, alkyl quaternary ammonium salts adds with the amount of 1 of HCFC-336 % by mole to 1.5 % by mole.In one embodiment, alkyl quaternary ammonium salts adds with the amount of 1 of HCFC-336 % by mole to 1.5 % by mole, and the weight of the nonionogenic tenside added is 1.0 to 2.0 times of the weight of alkyl quaternary ammonium salts.
In one embodiment, react and carry out at the temperature of about 60 to 90 DEG C.In another embodiment, react and carry out at 70 DEG C.
As used herein, alkaline aqueous solution is liquid (no matter solution, dispersion, emulsion or suspension etc.), and it mainly has the liquid, aqueous of the pH of more than 7.In certain embodiments, basic aqueous solution has the pH of more than 8.In certain embodiments, basic aqueous solution has the pH of more than 10.In certain embodiments, basic aqueous solution has the pH of 10-13.In certain embodiments, alkaline aqueous solution comprises a small amount of miscible or immiscible organic liquid with water.In certain embodiments, the liquid medium in alkaline aqueous solution is the water of at least 90%.In one embodiment, described water is tap water; In other embodiments, described water is deionized water or distilled water.
Alkali in alkaline aqueous solution is selected from basic metal, the oxyhydroxide of alkaline-earth metal, oxide compound, carbonate or phosphoric acid salt, and their mixture.In one embodiment, available alkali is lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide, magnesium oxide, calcium oxide, sodium carbonate, salt of wormwood, sodium phosphate, potassiumphosphate or their mixture.
For the synthesis of noticeable as foam expansion agent 1,1, Isosorbide-5-Nitrae, in some schemes of 4,4-hexafluoro-2-butylene, hydrogen perhaloalkenes HCFC-1326mxz is impurity.In the scheme that other is possible, it can be intermediate.A kind of method of synthesis HCFC-1326mxz is by 1,1, Isosorbide-5-Nitrae, the hydrogenation of 4,4-hexafluoro-2,3-dichloro-2-butene.No matter which kind of synthetic method, obtains the mixture about Z-and the E-steric isomer of double bond usually.Regrettably, it shows quite high toxicity, so no matter formed as impurity, or is formed as intermediate, all expects to convert it into available product with high yield.Dehydrochlorination will provide hexafluoro-2-butyne, and it is hydrogenatable to provide 1,1, Isosorbide-5-Nitrae, 4,4-hexafluoro-2-butylene.In classical organic chemistry, the dehydrochlorination forming the vinylchlorid of acetylene requires suitable exacting terms, such as very strong alkali, as the liquid ammonia solution of sodium.Report and used alkali aqueous solution at the temperature of 100-120 DEG C to the highest 200 or 250 DEG C, the polyfluoro vinylchlorid dehydrohalogenation of higher molecular weight can be made to become alkynes.But, at these tem-peratures, the vapour pressure that hexafluoro-2-butyne will have in too high reactor, and the impact being subject to degraded.
Find, alkaline aqueous solution and the combination as the alkyl quaternary ammonium salts of phase-transfer catalyst can be used, at the temperature far below 100 DEG C, by Z-and E-1,1, Isosorbide-5-Nitrae, the chloro-2-butylene dehydrochlorination of 4,4-hexafluoro-2-.
As used herein, phase-transfer catalyst is intended to represent and is conducive to ionic compound from containing aqueous phase or the material transferred to from solid phase organic phase.Described phase-transfer catalyst is conducive to the reaction of these different and incompatible components.Although different phase-transfer catalysts can act in a different manner, their mechanism of action does not determine their effectiveness in the present invention, and precondition is that described phase-transfer catalyst is conducive to dehydrochlorination reaction.
As used herein, phase-transfer catalyst is alkyl quaternary ammonium salts, and wherein said alkyl group is the alkyl chain with four to ten two carbon atoms.In one embodiment, alkyl quaternary ammonium salts is 4-butyl ammonium.The negatively charged ion of described salt can be that halogen ion is as chlorion or bromide anion, hydrogen sulfate ion or other conventional negatively charged ion any.
In another embodiment, alkyl quaternary ammonium salts is methyl tricapryl ammonium chloride (Aliquat336).In another embodiment, alkyl quaternary ammonium salts is four octyl group ammonium chlorides.In another embodiment, alkyl quaternary ammonium salts is four octyl sulfate hydrogen ammoniums.
Usually be construed to other compound of phase-transfer catalyst in other applications, comprise crown ether, cave ether or independent nonionogenic tenside, not there is the remarkably influenced of transformation efficiency on the dehydrochlorination reaction of same way or speed.
1,1, Isosorbide-5-Nitrae, Z-and the E-isomer of the chloro-2-butylene of 4,4-hexafluoro-2-shows visibly different reactivity relative to dehydrochlorination, and has different requirements for being used as effective phase-transfer catalyst in the reaction.Z-isomer
CF
3CCl＝CHCF
3
Dehydrochlorination Useful alkyls quaternary ammonium salt carry out, wherein said alkyl group is the alkyl chain with four to ten two carbon atoms.The negatively charged ion of described salt can be that halogen ion is as chlorion or bromide anion, hydrogen sulfate ion or other conventional negatively charged ion any.In one embodiment, alkyl quaternary ammonium salts is 4-butyl ammonium.In another embodiment, alkyl quaternary ammonium salts is tetrahexyl ammonium salt.In another embodiment, alkyl quaternary ammonium salts is four octyl group ammonium salts.In another embodiment, alkyl quaternary ammonium salts is methyl trioctylphosphine ammonium salt.
1,1, Isosorbide-5-Nitrae, the dehydrochlorination Useful alkyls quaternary ammonium salt of the E-isomer of the chloro-2-butylene of 4,4-hexafluoro-2-carries out, and wherein said alkyl group is alkyl chain, and described alkyl chain has at least one alkyl chain containing 8 or more carbon.In another embodiment, described alkyl quaternary ammonium salts has the alkyl chain that three have 8 or more carbon, such as methyl trioctylphosphine ammonium salt.In another embodiment, alkyl quaternary ammonium salts is four octyl group ammonium salts.In another embodiment, alkyl quaternary ammonium salts is four decyl ammonium salts.In another embodiment, alkyl quaternary ammonium salts is four (dodecyl) ammonium salt.The negatively charged ion of described salt can be that halogen ion is as chlorion or bromide anion, hydrogen sulfate ion or other conventional negatively charged ion any.
In another embodiment, 1,1, Isosorbide-5-Nitrae, the dehydrochlorination of the E-isomer of the chloro-2-butylene of 4,4-hexafluoro-2-can carry out with alkyl quaternary ammonium salts under the existence of nonionogenic tenside, and wherein said alkyl group is the alkyl chain with four to ten two carbon atoms.Described nonionogenic tenside can be ethoxylized nonylphenol class, and ethoxylation C12-C15 straight-chain fatty alcohol.Suitable nonionogenic tenside comprises from Stepan Company's
n25-9 and
10.
In one embodiment, alkyl quaternary ammonium salts is with 1,1, and Isosorbide-5-Nitrae, the amount of 0.5 % by mole to 2.0 % by mole of the chloro-2-butylene of 4,4-hexafluoro-2-adds.In another embodiment, alkyl quaternary ammonium salts is with 1,1, and Isosorbide-5-Nitrae, the amount of 1 % by mole to 2 % by mole of the chloro-2-butylene of 4,4-hexafluoro-2-adds.In another embodiment, alkyl quaternary ammonium salts is with 1,1, and Isosorbide-5-Nitrae, the amount of 1 % by mole to 1.5 % by mole of the chloro-2-butylene of 4,4-hexafluoro-2-adds.
In one embodiment, Z-or E-1,1, Isosorbide-5-Nitrae, the dehydrochlorination of the chloro-2-butylene of 4,4-hexafluoro-2-carries out under the existence of alkali halide salts.In one embodiment, basic metal is sodium or potassium.In one embodiment, halogen ion is chlorion or bromide anion.In one embodiment, alkali halide salts is sodium-chlor.Be not bound by any particular theory, it is believed that alkali halide salts makes phase-transfer catalyst stablize.Although dehydrochlorination reaction itself produces alkali metal chloride, specifically sodium-chlor, if sodium hydroxide is used as alkali, then add the effect that extra sodium-chlor provides the yield increasing hexafluoro-2-butyne further.
Add alkali halide salts and also reduce the fluorion amount measured in the current effluent of reaction.Be not bound by any particular theory, it is believed that the existence of fluorochemical is 1,1, Isosorbide-5-Nitrae, caused by the decomposition of the chloro-2-butylene raw material of 4,4-hexafluoro-2-or hexafluoro-2-butyne product.
In multiple sample, the fluorion amount be present in the current effluent of dehydrochlorination is about 6000ppm.In several instances, use every mole of phase-transfer catalyst 30 to 60 equivalent sodium-chlor, the fluorion amount in current effluent is reduced to 2000ppm.In one embodiment, alkali metal halide adds with every mole of phase-transfer catalyst 25 to 100 equivalent.In another embodiment, alkali metal halide adds with every mole of phase-transfer catalyst 30 to 75 equivalent.In another embodiment, alkali metal halide adds with every mole of phase-transfer catalyst 40 to 60 equivalent.
In one embodiment, react and carry out at the temperature of about 60 to 90 DEG C.In another embodiment, react and carry out at 70 DEG C.
As used herein, alkaline aqueous solution is liquid, and it mainly has liquid, aqueous (no matter it is solution, dispersion, emulsion or suspension etc.) of the pH of more than 7.In certain embodiments, basic aqueous solution has the pH of more than 8.In certain embodiments, basic aqueous solution has the pH of more than 10.In certain embodiments, basic aqueous solution has the pH of 10-13.In certain embodiments, alkaline aqueous solution comprises a small amount of miscible or immiscible organic liquid with water.In certain embodiments, the liquid medium in alkaline aqueous solution is the water of at least 90%.In one embodiment, described water is tap water; In other embodiments, described water is deionized water or distilled water.
Alkali in alkaline aqueous solution is selected from basic metal, the oxyhydroxide of alkaline-earth metal, oxide compound, carbonate or phosphoric acid salt, and their mixture.In one embodiment, available alkali is lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide, magnesium oxide, calcium oxide, sodium carbonate, salt of wormwood, sodium phosphate, potassiumphosphate or their mixture.
As used herein, term " comprises ", " comprising ", " containing ", " having " or their any other modification are all intended to contain comprising of nonexcludability.Such as, comprise the technique of key element list, method, goods or equipment and need not be only limitted to those key elements, but other key element that clearly do not list or that this type of technique, method, goods or equipment are intrinsic can be comprised.In addition, illustrate unless the contrary is explicitly, "or" refers to the "or" of inclusive, instead of refers to the "or" of exclusiveness.Such as, below in any one A or B:A that all satisfy condition be genuine (or existence) and B be false (or non-existent), A is false (or non-existent) and B is genuine (or existence) and A and B is all genuine (or existence).
Equally, " one " or " one " is used to describe key element described herein and component.Do like this and be only conveniently and general sense is provided to scope of the present invention.This description should be understood to include one or at least one, unless and refer else significantly, odd number also comprises plural number.
Unless otherwise defined, what all technology used herein and the implication of scientific terminology were all understood usually with those skilled in the art is the same.Although all can be used for practice or the inspection of the embodiment of the present invention with the fellow of those methods as herein described and material or equivalent, suitable method and material are as mentioned below those.If conflict occurs, be then as the criterion with this specification sheets (comprising definition).In addition, material, method and example are only illustrative, and are not intended to limit.
example
Concept described herein will further describe in following Examples, and described example does not limit the scope of the present invention described in claim.
Tetra-n-butyl ammonium bromide (TBAB), 4-n-butyl ammonium hydrogen sulfate, methyl tricapryl ammonium chloride (
336), four octyl group ammonium chlorides (TOAC), four octyl sulfate hydrogen ammoniums (TOAHS) and methyl tributyl brometo de amonio (TBMAB) are purchased from Sigma Aldrich (St.Louis, MO).
n25-9 and
10 purchased from Stepan Company (Northfield, Illinois); 1326 purchased from Synquest Labs, Inc..
legend
HCFC-336mfa is CF
3cCl
2cH
2cF
3
HCFC-336mdd is CF
3cHClCHClCF
3
HCFC-1326mxy is CF
3cCl=CHCF
3
HFB is CF
3c ≡ CCF
3
example 1
Example 1 to illustrate under the existence of Aliquat 336 336mdd to the transformation efficiency of hexafluoro butine.
At room temperature exist
under the existence of 336 (0.53g, 0.001325mol), the NaOH aqueous solution (22mL, 0.22mol) is added in 336mdd (23.5g, 0.1mol) and water (5.6mL).After addition, make temperature of reaction be increased to 70 DEG C, and use vapor-phase chromatography to monitor this reaction.React completely after 2 hours, and in dry ice trap, collect 14g product (transformation efficiency: 100%; Yield: 86%).
example 2
Example 2 to illustrate under the existence of Aliquat 336 336mfa to the transformation efficiency of hexafluoro-2-butyne.
At room temperature exist
under the existence of 336 (0.53g, 0.001325mol), the NaOH aqueous solution (22mL, 0.22mol) is added in 336mfa (23.5g, 0.1mol) and water (5.6mL).After addition, make temperature of reaction be increased to 70 DEG C, and use vapor-phase chromatography to monitor this reaction.React completely and in dry ice trap, collect hexafluoro butine after 2 hours.
example 3
Example 3 illustrates under the existence of tetrabutylammonium chloride and nonionogenic tenside, and 336mfa is to the transformation efficiency of hexafluoro-2-butyne.
At room temperature at Tetrabutyl amonium bromide (0.45g, 0.001325mol) and
under the existence of 10 (0.7g), the NaOH aqueous solution (22mL, 0.22mol) is added in 336mfa (23.5g, 0.1mol) and water (5.6mL).After addition, make temperature of reaction be increased to 70 DEG C, and use vapor-phase chromatography to monitor this reaction.React completely and in dry ice trap, collect hexafluoro butine after 4.5 hours.
comparative example 1
The NaOH aqueous solution (23mL, 0.23mol) is added HCFC-336mfa (23.5g, 0.1mol) at 37 DEG C with the mixture of water (18mL).After addition, make temperature of reaction be increased to 70 DEG C, and use vapor-phase chromatography to monitor this reaction.After 31 hours, in dry ice trap, collect 0.36g hexafluoro-2-butyne (transformation efficiency: 2.2%; Yield: 2.2%).
comparative example 2
Under the existence of 15-crown ether-5 (0.65g, 0.003mol), at 37 DEG C, the NaOH aqueous solution (10mL, 0.10mol) is added HCFC-336mfa (11.8g, 0.05mol) with the mixture of water (18mL).After addition, make temperature of reaction be increased to 70 DEG C, and use vapor-phase chromatography to monitor this reaction.After 30 hours, reaction not exclusively.1.16g hexafluoro-2-butyne (transformation efficiency: 14% is collected in dry ice trap; Yield: 14%).
comparative example 3
?
under the existence of 10 (0.7g), at 37 DEG C, the NaOH aqueous solution (22mL, 0.22mol) is added in HCFC-336mfa (23g, 0.1mol) and water (18mL).After addition, make temperature of reaction be increased to 70 DEG C, and use vapor-phase chromatography to monitor this reaction.After 22 hours, reaction not exclusively.1.09g hexafluoro-2-butyne (transformation efficiency: 17% is collected in dry ice trap; Yield: 6.8%).
example 4
At 35 DEG C, under the existence of tetra-n-butyl ammonium bromide (0.45g, 0.001325mol), the NaOH aqueous solution (12mL, 0.12mol) is added Z-1326 (20g, 0.1mol) with the mixture of water (18mL).After addition, make temperature of reaction be increased to 70 DEG C, and use vapor-phase chromatography to monitor this reaction.React completely after 1 hour, and in dry ice trap, collect 15.4g product (transformation efficiency: 100%; Yield: 95%).
example 5
At 35 DEG C, under the existence of 4-n-butyl ammonium hydrogen sulfate (0.43g, 0.001325mol), by the NaOH aqueous solution (12mL, 0.12mol) add in the mixture of Z-1326 (20g, 0.1mol) and water (18mL).After addition, make temperature of reaction be increased to 70 DEG C, and use vapor-phase chromatography to monitor this reaction.React completely after 1 hour, and in dry ice trap, collect 11g product (transformation efficiency: 100%; Yield: 71%).
example 6
At 35 DEG C,
under the existence of 336 (0.53g, 0.001325mol), the NaOH aqueous solution (12mL, 0.12mol) is added Z-1326 (20g, 0.1mol) with the mixture of water (18mL).After addition, make temperature of reaction be increased to 70 DEG C, and use vapor-phase chromatography to monitor this reaction.React completely after 1 hour, and in dry ice trap, collect 15.6g product (transformation efficiency: 100%; Yield: 96%).
example 7
At 42 DEG C,
under the existence of 336 (0.53g, 0.001325mol), the NaOH aqueous solution (12mL, 0.12mol) is added E-1326 (20g, 0.1mol) with the mixture of water (18mL).After addition, make temperature of reaction be increased to 70 DEG C, and use vapor-phase chromatography to monitor this reaction.React completely after 1 hour, and in dry ice trap, collect 15.8g product (transformation efficiency: 100%; Yield: 98%).
example 8
At 42 DEG C, under the existence of tetra-n-butyl ammonium bromide (0.45g, 0.001325mol), the NaOH aqueous solution (12mL, 0.12mol) is added E-1326 (20g, 0.1mol) with the mixture of water (18mL).After addition, make temperature of reaction be increased to 70 DEG C, and use vapor-phase chromatography to monitor this reaction.After seven hours, reaction not exclusively.12.6g product (transformation efficiency: 78% is collected in dry ice trap; Yield: 78%).
example 9
At 42 DEG C, under the existence of 4-n-butyl ammonium hydrogen sulfate (0.43g, 0.001325mol), by the NaOH aqueous solution (12mL, 0.12mol) add E-1326 (20g, 0.1mol) with the mixture of water (18mL).After addition, make temperature of reaction be increased to 70 DEG C, and use vapor-phase chromatography to monitor this reaction.After seven hours, reaction not exclusively.12.6g product (transformation efficiency: 77% is collected in dry ice trap; Yield: 77%).
example 10
At 42 DEG C, under the existence of four octyl group brometo de amonios (0.72g, 0.001325mol), the NaOH aqueous solution (12mL, 0.12mol) is added E-1326 (20g, 0.1mol) with the mixture of water (18mL).After addition, make temperature of reaction be increased to 70 DEG C, and use vapor-phase chromatography to monitor this reaction.React completely after 6.5 hours.15.6g product (transformation efficiency: 100% is collected in dry ice trap; Yield: 95%).
example 11
At 42 DEG C, under the existence of four octyl group ammonium chlorides (0.43g, 0.001325mol), the NaOH aqueous solution (12mL, 0.12mol) is added E-1326 (20g, 0.1mol) with the mixture of water (18mL).After addition, make temperature of reaction be increased to 70 DEG C, and use vapor-phase chromatography to monitor this reaction.After 5.5 hours, in dry ice trap, collect 15.2g product (transformation efficiency: 95%; Yield: 93%).
example 12
At 42 DEG C, under the existence of tetrabutylammonium chloride (0.37g, 0.001325mol), the NaOH aqueous solution (12mL, 0.12mol) is added E-1326 (20g, 0.1mol) with the mixture of water (18mL).After addition, make temperature of reaction be increased to 70 DEG C, and use vapor-phase chromatography to monitor this reaction.After 23 hours, in dry ice trap, collect 14.8g product (transformation efficiency: 90%; Yield: 87%).
example 13
At 42 DEG C, under the existence of methyltributylammonichloride chloride (0.31g, 0.001325mol), by the NaOH aqueous solution (12mL, 0.12mol) add E-1326 (20g, 0.1mol) with the mixture of water (18mL).After addition, make temperature of reaction be increased to 70 DEG C, and use vapor-phase chromatography to monitor this reaction.After 23 hours, in dry ice trap, collect 8g product (transformation efficiency: 59%; Yield: 49%).
example 14
At 38 DEG C, at Tetrabutyl amonium bromide (0.45g, 0.001325mol) and
under the existence of N25-9 (0.7g), the NaOH aqueous solution (12mL, 0.12mol) is added ZE-1326 (20g, 0.1mol) with the mixture of water (18mL).After addition, make temperature of reaction be increased to 70 DEG C, and use vapor-phase chromatography to monitor this reaction.React completely after 5 hours.13g product (transformation efficiency: 100% is collected in dry ice trap; Yield: 80%).
example 15
At 38 DEG C, at Tetrabutyl amonium bromide (0.45g, 0.001325mol) and
under the existence of 10 (0.7g), the NaOH aqueous solution (12mL, 0.12mol) is added ZE-1326 (20g, 0.1mol) with the mixture of water (18mL).After addition, make temperature of reaction be increased to 70 DEG C, and use vapor-phase chromatography to monitor this reaction.React completely after 5 hours.11.2g product (transformation efficiency: 100% is collected in dry ice trap; Yield: 69%).
example 16
At 37 DEG C, at NaCl (2.3g, 0.0393mol) and
under the existence of 336 (0.53g, 0.001325mol), through 30 minutes, the 10M NaOH aqueous solution (12mL, 0.12mol) is added in ZE-1326 (20g, 0.1mol) and water (18mL).Upon complete addition, after addition, make temperature of reaction be increased to 70 DEG C, and use vapor-phase chromatography to monitor this reaction.Reacted completely after 1 hour 20 minutes, and submit to water layer to be used for weight-percent fluoride analysis.
example 17
At 37 DEG C, at NaCl (4.6g, 0.0786mol) and
under the existence of 336 (0.53g, 0.001325mol), through 30 minutes, the NaOH aqueous solution (12mL, 0.12mol) is added in ZE-1326 (20g, 0.1mol) and water (18mL).Upon complete addition, after addition, make temperature of reaction be increased to 70 DEG C, and use vapor-phase chromatography to monitor this reaction.Reacted completely after 1 hour 20 minutes, and submit to water layer to be used for weight-percent fluoride analysis.
example 18
At 37 DEG C, at NaCl (3.45g, 0.0590mol) and
under the existence of 336 (0.53g, 0.001325mol), the NaOH aqueous solution (12mL, 0.12mol) was added in the mixture of ZE-1326 (20g, 0.1mol) and water (18mL) through 30 minutes.Upon complete addition, after addition, make temperature of reaction be increased to 70 DEG C, and use vapor-phase chromatography to monitor this reaction.React completely after 2 hours, and submit to water layer to be used for weight-percent fluoride analysis.
comparative example 4
At 37 DEG C, the NaOH aqueous solution (12mL, 0.12mol) is added in the mixture of ZE-1326 (20g, 0.1mol) and water (18mL).After addition, make temperature of reaction be increased to 70 DEG C, and use vapor-phase chromatography to monitor this reaction.After 31 hours, in dry ice trap, collect 0.36g product (transformation efficiency: 2.2%; Yield: 2.2%).
comparative example 5
Under the existence of 15-crown ether-5 (0.65g, 0.003mol), at 37 DEG C, the NaOH aqueous solution (6mL, 0.06mol) is added ZE-1326 (10g, 0.05mol) with the mixture of water (18mL).After addition, make temperature of reaction be increased to 70 DEG C, and use vapor-phase chromatography to monitor this reaction.After 30 hours, reaction not exclusively.1.16g product (transformation efficiency: 14% is collected in dry ice trap; Yield: 14%).
comparative example 6
?
under the existence of 10 (0.7g), at 37 DEG C, the NaOH aqueous solution (12mL, 0.12mol) is added in the mixture of ZE-1326 (20g, 0.1mol) and water (18mL).After addition, make temperature of reaction be increased to 70 DEG C, and use vapor-phase chromatography to monitor this reaction.After 22 hours, reaction not exclusively.1.09g product (transformation efficiency: 17% is collected in dry ice trap; Yield: 6.8%).
table 1:
* 1326 add in KOH
Generally above to describe or behavior described in example is all necessary it is noted that not all, a part of concrete behavior is optional, and except described those, also can implement other behaviors one or more.In addition, the order of listed behavior needs not to be the order that they are implemented.
In the above specification, different concepts is described with reference to specific embodiment.But those of ordinary skill in the art recognizes and can make multiple amendment and modification when not departing from the scope of the invention shown in following claim.Therefore, specification sheets and accompanying drawing should be considered to exemplary and nonrestrictive, and this type of modification all are all intended to be included in scope of the present invention.
Below the solution of beneficial effect, other advantage and problem is described for specific embodiment.But, the solution of beneficial effect, advantage, problem and any beneficial effect, advantage or solution can be caused to produce or become any one or more features more significant and may not be interpreted as the key of any or all claim, required or essential characteristic.
Will be appreciated that, for clarity sake, some feature described in context of different embodiment also can provide in a joint manner in single embodiment herein.Otherwise for simplicity's sake, the various features described in the context of single embodiment also can provide separately or with any sub-portfolio.In addition, the correlation values proposed in scope comprises each value in described scope.
Claims (16)
1. the method for the preparation of hexafluoro-2-butyne, described method comprises: in the presence of a phase transfer catalyst, makes the reactant aqueous solution of chlorination reaction thing and alkali metal hydroxide, and described phase-transfer catalyst comprises at least one alkyl group, described alkyl group has at least 8 carbon, and reclaim described hexafluoro-2-butyne, wherein two chloro-1,1,1, the transformation efficiency of 4,4,4-hexafluoro butane is per hour at least 50%.
2. method according to claim 1, wherein said phase-transfer catalyst is alkyl quaternary ammonium salts, and wherein said phase-transfer catalyst has at least 3 alkyl groups, and described alkyl group has eight or more carbon.
3. method according to claim 1, wherein said alkyl quaternary ammonium salts is methyl tricapryl ammonium chloride.
4. method according to claim 1, wherein said alkaline aqueous solution is made by being selected from following alkali: lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide, magnesium oxide, calcium oxide, sodium carbonate, salt of wormwood, sodium phosphate, potassiumphosphate and their mixture.
5. method according to claim 1, wherein said chlorination reaction thing is chlorine fluorine butane or chlorine fluorine butylene.
6. method according to claim 1, wherein said chlorination reaction thing is HCFC-336mdd (2,3-bis-chloro-1,1, Isosorbide-5-Nitrae, 4,4-hexafluoro butane), HCFC-336mfa (2,2-bis-chloro-1,1, Isosorbide-5-Nitrae, 4,4--hexafluoro butane) or HCFO-1326mxz (E-or Z-1,1,1, the chloro-2-butylene of 4,4,4-hexafluoro-2-).
7. the method for the preparation of hexafluoro-2-butyne, described method comprises: have containing under the alkyl group of four to ten carbon atoms and the alkyl quaternary ammonium salts of their mixture and the existence of nonionogenic tenside, make the reactant aqueous solution of chlorination reaction thing and alkali metal hydroxide, and reclaim described hexafluoro-2-butyne, and wherein two chloro-1,1,1,4,4,4-hexafluoro butane is per hour at least 20% to the transformation efficiency of hexafluoro-2-butyne.
8. method according to claim 8, wherein said nonionogenic tenside is selected from ethoxylized nonylphenol class and ethoxylation C12-C15 fatty alcohol.
9. method according to claim 8, wherein said alkyl quaternary ammonium salts be following at least one: tetrabutylammonium chloride, Tetrabutyl amonium bromide, 4-butyl ammonium hydrogen sulfate, four octyl group ammonium chlorides, four octyl group brometo de amonios, four octyl sulfate hydrogen ammoniums, methyl tricapryl ammonium chloride, methyl trioctylphosphine brometo de amonio, four decyl ammonium chlorides, four decyl brometo de amonios and four (12) alkyl ammomium chloride.
10. method according to claim 8, wherein said alkyl quaternary ammonium salts is 4-butyl ammonium.
11. methods according to claim 8, wherein said alkyl quaternary ammonium salts is methyl trioctylphosphine ammonium salt.
12. methods according to claim 8, wherein said alkaline aqueous solution is made by being selected from following alkali: lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide, magnesium oxide, calcium oxide, sodium carbonate, salt of wormwood, sodium phosphate, potassiumphosphate and their mixture.
13. methods according to claim 6, wherein said alkyl quaternary ammonium salts is 4-butyl ammonium, and described nonionogenic tenside is ethoxylized nonylphenol class.
14. methods according to claim 8, wherein said chlorination reaction thing is chlorine fluorine butane or chlorine fluorine butylene.
15. methods according to claim 8, wherein said chlorination reaction thing is HCFC-336mdd (2,3-bis-chloro-1,1, Isosorbide-5-Nitrae, 4,4-hexafluoro butane), HCFC-336mfa (2,2-bis-chloro-1,1, Isosorbide-5-Nitrae, 4,4--hexafluoro butane) or HCFO-1326mxz (E-or Z-1,1,1, the chloro-2-butylene of 4,4,4-hexafluoro-2-).
16. methods according to claim 1 or 8, the described step wherein making described chlorination reaction thing react is carried out under the existence of alkali metal halide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810409549.4A CN108530261A (en) | 2012-09-28 | 2013-09-27 | The dehydrochlorination of chlorination reaction object is to prepare 1,1,1,4,4,4- hexafluoro -2- butine |
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US201261707220P | 2012-09-28 | 2012-09-28 | |
| US201261707231P | 2012-09-28 | 2012-09-28 | |
| US61/707220 | 2012-09-28 | ||
| US61/707231 | 2012-09-28 | ||
| PCT/US2013/062080 WO2014052695A1 (en) | 2012-09-28 | 2013-09-27 | Dehydrochlorination of chlorinated reactants to produce 1,1,1,4,4,4-hexafluoro-2-butyne |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810409549.4A Division CN108530261A (en) | 2012-09-28 | 2013-09-27 | The dehydrochlorination of chlorination reaction object is to prepare 1,1,1,4,4,4- hexafluoro -2- butine |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN104684877A true CN104684877A (en) | 2015-06-03 |
Family
ID=49354928
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810409549.4A Pending CN108530261A (en) | 2012-09-28 | 2013-09-27 | The dehydrochlorination of chlorination reaction object is to prepare 1,1,1,4,4,4- hexafluoro -2- butine |
| CN201380050238.9A Pending CN104684877A (en) | 2012-09-28 | 2013-09-27 | Dehydrochlorination of chlorinated reactants to produce 1,1,1,4,4,4-hexafluoro-2-butyne |
Family Applications Before (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810409549.4A Pending CN108530261A (en) | 2012-09-28 | 2013-09-27 | The dehydrochlorination of chlorination reaction object is to prepare 1,1,1,4,4,4- hexafluoro -2- butine |
Country Status (7)
| Country | Link |
|---|---|
| EP (1) | EP2922809A1 (en) |
| JP (1) | JP6272877B2 (en) |
| KR (1) | KR102147909B1 (en) |
| CN (2) | CN108530261A (en) |
| IN (1) | IN2015DN01199A (en) |
| MX (1) | MX371333B (en) |
| WO (1) | WO2014052695A1 (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106349007A (en) * | 2016-08-22 | 2017-01-25 | 巨化集团技术中心 | Preparation method of Z-HFO-1336 |
| CN110950735A (en) * | 2019-10-22 | 2020-04-03 | 浙江巨化技术中心有限公司 | Method for preparing 1,1,1,4,4, 4-hexafluoro-2-butyne by gas phase method |
| CN113454052A (en) * | 2019-02-21 | 2021-09-28 | 大金工业株式会社 | Method for producing halogenated olefin compound and fluorinated alkyne compound |
| CN113939492A (en) * | 2019-04-05 | 2022-01-14 | 科慕埃弗西有限公司 | Process for preparing Z-1,1,1,4,4, 4-hexafluorobut-2-ene and intermediates useful for preparing same |
| CN115210202A (en) * | 2020-03-04 | 2022-10-18 | 科慕埃弗西有限公司 | Process for preparing (Z) -1,1,1,4,4,4-hexafluoro-2-butene and intermediates |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9440896B2 (en) | 2012-09-28 | 2016-09-13 | The Chemours Company Fc, Llc | Dehydrochlorination of HCFC-336 isomers to 1,1,1,4,4,4-hexafluoro-2-butyne |
| EP3102556B1 (en) * | 2014-02-07 | 2023-03-29 | The Chemours Company FC, LLC | Integrated process for the production of z-1,1,1,4,4,4-hexafluoro-2-butene |
| US9328042B2 (en) | 2014-08-11 | 2016-05-03 | The Chemours Company Fc, Llc | Integrated process for the production of Z-1,1,1,4,4,4-hexafluoro-2-butene |
| KR20200032093A (en) | 2017-07-27 | 2020-03-25 | 더 케무어스 컴퍼니 에프씨, 엘엘씨 | (Z) -1,1,1,4,4,4-hexafluoro-2-butene production method |
| WO2020171011A1 (en) * | 2019-02-21 | 2020-08-27 | ダイキン工業株式会社 | Halogenated alkene compound and method for manufacturing fluorinated alkyne compound |
| EP3947326A1 (en) * | 2019-04-05 | 2022-02-09 | The Chemours Company FC, LLC | Processes for producing z-1,1,1,4,4,4-hexafluorobut-2-ene and intermediates for producing same |
| WO2020206279A1 (en) * | 2019-04-05 | 2020-10-08 | The Chemours Company Fc, Llc | Processes for producing z-1,1,1,4,4,4-hexafluorobut-2-ene and intermediates for producing same |
| CN110845296A (en) * | 2019-12-12 | 2020-02-28 | 岳阳市宇恒化工有限公司 | Method for preparing alkynyl compound |
| CN114409514B (en) * | 2021-12-21 | 2023-07-18 | 西安近代化学研究所 | Synthesis method of 1, 4-hexafluoro-2-butanone |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101675017A (en) * | 2007-04-17 | 2010-03-17 | 中央硝子株式会社 | Method for producing 3,3,3-trifluoropropyne |
| CN101796002A (en) * | 2007-09-11 | 2010-08-04 | 大金工业株式会社 | Process for producing 2,3,3,3-tetrafluoropropene |
| US20110288346A1 (en) * | 2010-05-21 | 2011-11-24 | Honeywell International Inc. | Process for cis 1,1,1,4,4,4-hexafluoro-2-butene |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6210027A (en) * | 1985-07-08 | 1987-01-19 | Daikin Ind Ltd | Production of 2-trifluoromethyl-3,3,3-trifluoropropene |
| US6548719B1 (en) * | 2001-09-25 | 2003-04-15 | Honeywell International | Process for producing fluoroolefins |
| JP2010037205A (en) * | 2008-07-31 | 2010-02-18 | Nippon Zeon Co Ltd | Fluorinated alkane compound, method of preparing the same, and method of preparing perfluoroalkyne compound |
| US8667404B2 (en) * | 2008-08-06 | 2014-03-04 | Autodesk, Inc. | Predictive material editor |
-
2013
- 2013-09-27 KR KR1020157007748A patent/KR102147909B1/en active IP Right Grant
- 2013-09-27 MX MX2015003797A patent/MX371333B/en active IP Right Grant
- 2013-09-27 JP JP2015534687A patent/JP6272877B2/en active Active
- 2013-09-27 WO PCT/US2013/062080 patent/WO2014052695A1/en active Application Filing
- 2013-09-27 EP EP13776644.0A patent/EP2922809A1/en not_active Withdrawn
- 2013-09-27 CN CN201810409549.4A patent/CN108530261A/en active Pending
- 2013-09-27 CN CN201380050238.9A patent/CN104684877A/en active Pending
-
2015
- 2015-02-13 IN IN1199DEN2015 patent/IN2015DN01199A/en unknown
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101675017A (en) * | 2007-04-17 | 2010-03-17 | 中央硝子株式会社 | Method for producing 3,3,3-trifluoropropyne |
| CN101796002A (en) * | 2007-09-11 | 2010-08-04 | 大金工业株式会社 | Process for producing 2,3,3,3-tetrafluoropropene |
| US20110288346A1 (en) * | 2010-05-21 | 2011-11-24 | Honeywell International Inc. | Process for cis 1,1,1,4,4,4-hexafluoro-2-butene |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106349007A (en) * | 2016-08-22 | 2017-01-25 | 巨化集团技术中心 | Preparation method of Z-HFO-1336 |
| WO2018036076A1 (en) * | 2016-08-22 | 2018-03-01 | 王宗令 | Preparation method for z-hfo-1336 |
| CN106349007B (en) * | 2016-08-22 | 2019-06-11 | 巨化集团技术中心 | A kind of preparation method of Z-HFO-1336 |
| CN113454052A (en) * | 2019-02-21 | 2021-09-28 | 大金工业株式会社 | Method for producing halogenated olefin compound and fluorinated alkyne compound |
| CN113939492A (en) * | 2019-04-05 | 2022-01-14 | 科慕埃弗西有限公司 | Process for preparing Z-1,1,1,4,4, 4-hexafluorobut-2-ene and intermediates useful for preparing same |
| US11912639B2 (en) | 2019-04-05 | 2024-02-27 | The Chemours Company Fc, Llc | Processes for producing Z-1,1,1,4,4,4-hexafluorobut-2-ene and intermediates for producing same |
| CN113939492B (en) * | 2019-04-05 | 2024-05-17 | 科慕埃弗西有限公司 | Process for preparing Z-1, 4-hexafluorobut-2-ene and intermediates for preparing the same |
| CN110950735A (en) * | 2019-10-22 | 2020-04-03 | 浙江巨化技术中心有限公司 | Method for preparing 1,1,1,4,4, 4-hexafluoro-2-butyne by gas phase method |
| CN115210202A (en) * | 2020-03-04 | 2022-10-18 | 科慕埃弗西有限公司 | Process for preparing (Z) -1,1,1,4,4,4-hexafluoro-2-butene and intermediates |
Also Published As
| Publication number | Publication date |
|---|---|
| IN2015DN01199A (en) | 2015-06-26 |
| KR102147909B1 (en) | 2020-08-25 |
| KR20150061638A (en) | 2015-06-04 |
| WO2014052695A1 (en) | 2014-04-03 |
| MX2015003797A (en) | 2015-07-14 |
| JP6272877B2 (en) | 2018-01-31 |
| CN108530261A (en) | 2018-09-14 |
| MX371333B (en) | 2020-01-27 |
| JP2015530417A (en) | 2015-10-15 |
| EP2922809A1 (en) | 2015-09-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104684877A (en) | Dehydrochlorination of chlorinated reactants to produce 1,1,1,4,4,4-hexafluoro-2-butyne | |
| KR101868766B1 (en) | Process for producing 1-chloro-2,3,3-trifluoropropene | |
| US7951982B2 (en) | Method for producing fluorinated organic compounds | |
| KR102116848B1 (en) | Compositions comprising 1,1,1,2,3-pentafluoropropane or 2,3,3,3- tetrafluoropropene | |
| US9079818B2 (en) | Process for synthesis of fluorinated olefins | |
| US8927791B2 (en) | Method for producing tetrafluoropropenes | |
| CN101535227A (en) | Process to manufacture 2,3,3,3-tetrafluoropropene | |
| CN104936935A (en) | Synthesis of 3, 3, 3-trifluoropropyne | |
| CN102421728B (en) | Processes for reducing the amount of monofluoroacetate in hydrofluoroolefin production | |
| JP6995108B2 (en) | Methods for Producing Halogenated Olefin | |
| US9440896B2 (en) | Dehydrochlorination of HCFC-336 isomers to 1,1,1,4,4,4-hexafluoro-2-butyne | |
| WO2019067883A1 (en) | Synthesis and prepapration of 2, 3-dibromo-2-propen-1-ol | |
| WO2008027602A2 (en) | Production processes for making 1,1,1,2,2,3-hexafluoropropane | |
| JP2022539588A (en) | Compositions and methods for the synthesis of 2,3-dichloro-1,1,1,2-tetrafluoropropane and 2,3,3,3-tetrafluoropropene | |
| WO2015050953A1 (en) | Dehydrofluorination process to manufacture hydrofluoroolefins | |
| WO2019220463A1 (en) | Preparation of 2,3,3,3-tetrafluoropropene, intermediate and composition thereof | |
| CN113677650B (en) | Process for preparing Z-1, 4-hexafluorobut-2-ene and intermediates for preparing the same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20171228 Address after: Delaware, USA Applicant after: Como Efsee Co.,Ltd. Address before: Wilmington, Delaware, USA Applicant before: E. I. du Pont de Nemours and Co. |
|
| TA01 | Transfer of patent application right | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20150603 |
|
| RJ01 | Rejection of invention patent application after publication |