CA1122597A - Cyclic hydrocarbon perfluorination process - Google Patents
Cyclic hydrocarbon perfluorination processInfo
- Publication number
- CA1122597A CA1122597A CA297,549A CA297549A CA1122597A CA 1122597 A CA1122597 A CA 1122597A CA 297549 A CA297549 A CA 297549A CA 1122597 A CA1122597 A CA 1122597A
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- CA
- Canada
- Prior art keywords
- reaction zone
- process according
- boiling point
- polycyclic hydrocarbon
- perfluorination
- 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.)
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Classifications
-
- 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
- C07C23/18—Polycyclic halogenated hydrocarbons
- C07C23/20—Polycyclic halogenated hydrocarbons with condensed rings none of which is aromatic
- C07C23/38—Polycyclic halogenated hydrocarbons with condensed rings none of which is aromatic with three condensed rings
-
- 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
- C07C23/00—Compounds containing at least one halogen atom bound to a ring other than a six-membered aromatic ring
- C07C23/18—Polycyclic halogenated hydrocarbons
- C07C23/20—Polycyclic halogenated hydrocarbons with condensed rings none of which is aromatic
-
- 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
- C07C23/18—Polycyclic halogenated hydrocarbons
- C07C23/20—Polycyclic halogenated hydrocarbons with condensed rings none of which is aromatic
- C07C23/32—Polycyclic halogenated hydrocarbons with condensed rings none of which is aromatic with a bicyclo ring system containing eight carbon atoms
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Paper (AREA)
Abstract
ABSTRACT OF THE DISCLOSURE
Perfluorinated polycyclic hydrocarbons may be produced in high yield by a three-stage process comprising contacting a cyclic hydrocarbon such as an alkyladamantane with a fluoride of silver, manganese, sulfur or the like under vary-ing reaction conditions, generally in the liquid state, to provide a partially fluorinated cyclic hydrocarbon. This fluorination is followed by a second stage vapor phase reaction with a fluoride of cobalt, manganese, silver or the like at temperatures generally just above the boiling point of the ma-terial to yield highly fluorinated cyclic compounds, followed by a third stage reaction with the same reagent at substantially higher temperatures to provide the desired perfluorinated material.
Perfluorinated polycyclic hydrocarbons may be produced in high yield by a three-stage process comprising contacting a cyclic hydrocarbon such as an alkyladamantane with a fluoride of silver, manganese, sulfur or the like under vary-ing reaction conditions, generally in the liquid state, to provide a partially fluorinated cyclic hydrocarbon. This fluorination is followed by a second stage vapor phase reaction with a fluoride of cobalt, manganese, silver or the like at temperatures generally just above the boiling point of the ma-terial to yield highly fluorinated cyclic compounds, followed by a third stage reaction with the same reagent at substantially higher temperatures to provide the desired perfluorinated material.
Description
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BACKGROUND OF -THE INVENTION
This invention relates to an improved process for the fluorination of polycyclic hydrocarbons. More particularly, this invention relates to an improved method for the florination, preferably perfluorination, of said hydrocarbons using a three-stage reaction which effectively eliminates the production of unwanted by-products.
U.S. Patent No. 3,6~1,167, as well as United States Patent 4,041,086 disclosure a one-staga method for making perfluoroalkyladamantanes. Recent data using new analytical techniques now show that under the reaction conditions employed therein, using CoF3 and high tempexature, degradation of the non-florinated cyclic structure does result, with the formation of ring-opened products.
SUM~RY OF THE INVENTION
In accordance with the present invention, it has now been found that polycyclic hydrocarbons may be perfluorinated with substantially no degradation o the cyclic structure by ~1) partially fluorinating the starting cyclic compound with a mild fluorinating agent under moderate conditions in a first stage, followed by (2) reacting said partially fluorinated material in a second stage in the presence of a strong fluorinating agent at temperatures just above the boiling point of said material to provide a highly fluorinated compound; and thereafter (3) recycling said highly fluorinated compound into the same second stage reactor at considerably higher temperatures to provide an essentially perfluorinated polycyclic hydrocarbon free of any degradation ring-opened products.
~ll;ZZ597 There is thus provided, in accordance with the present teachings, a process for the perfluorination of non-aromatizable polycyclic hydrocar~ons which process comprises:
a) partially fluorinating a polycyclic hydrocarbon or the carbonyl, hydroxyl, chlorinated, or brominated derivative thereof, by contacting it in a first reaction zone wi*h a fluorinating agent selected from the group consisting of HF, HF-pyridine, AgF2, MnF3, SF4, ~bF5, KCoF4 and fluoroolefins, in the liquid phase under conditions sufficient to provide not more than about 50%
fluorination corresponding to perfluorination; and b) thereafter further fluorinating the partially fluorinated polycyclic hydrocarbon in the vapor phase in a second reaction zone with CoF3 at a temperature of no greater than about 50 C~ above the boiling point of the fluorinated material to provide a highly fluorinated material having a degree of fluorination corresponding to about 75-95% of perfluorination.
As an optional step in the process, the highly fluorinated material is recovered and recycled to the second reaction zone for recontact with CoF3 in the vapor phase at a temperature about 100 higher than was first employed in step b) to provide a substantially perfluorinated polycyclic hydro-carbon.
DESCRIPTION OF THE INVENTION
-The starting materials for this improved perfluorina-tion process comprise non-aromatizable polycyclic hydrocarbons selected from the group consisting of alkyladamantanes, as des-cribed in U.S. Patent 3,6~1,167, and having from 11-30 carbon atoms, preferably 12-14 carbon atoms, such as 1~3-dimethylada-` llZZ597 mantane, 1,3,5-trimethyladam~ntane, l-ethyladamantane, l-methyl-adamantane, l-ethyl-3-methyladamantane, l-ethyl, 3,5-dimethyladamantane, or the like; endo-and exo-tetrahydro-dicyclopentadiene; methanodecalins such as 1, 4-methanodecalin or 1,4,5,8-dimethanodecalin; hydrogenated pinane; camphane;
bi-cyclooctanes; bicyclononanes; and the like. When these compounds are treated in accordance with the process of this invention, there are obtained the corresponding perfluorinated polycyclic materials in high yield and purity, wherein at least 95% of the hydrogen atoms, and more preferably 97% to ......
7 ~
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100%, are replaced by fluorine atoms. Generally, with this improved process, the conversion of the starting material to the corresponding perfluorinted compound is at least 50%, and most usually about 90% or more.
These perfluorin~ted materials are useful in a variety of industrial and pharmaceutical applications. The fluorinated alkyladamantanes, for example, are useful as gas turbine engine coolants, dielectric coolants for transformers, generators, and the like, as well as components in synthetic blood compositions, perfusion media, and like bi~logical applications. The perfluorinated cyclic materials are also useful as working fluids in heat pipes and Rankill cycle engines.
The first stage~of the aforedescribed process to provide a partially fluorinated intermediate is conveniently carried out by contacting the polycyclic hydrocarbon or their hydroxylated or carboxylated derivatives depending on the fluorinating agent used, in the liquid phase with a fluorinatin~ a~ent selected from the group consisting of HF, HF-pyridine complex, AgF2~ MnF3, SF4, SbF5, KCoF4, and fluoroolefins, under vary^ing conditions of temperature~
pressure, and the like, depending upon the nature of the starting material and fluorinating agent employed. These fluorinating agents are much milder in their action than CoF3 on hydrocarbons. Consequently, the degree of fluorination can be controlled by the proper selection of agent and starting material. Generally, the incorporation of from about 3 to 6 fluorine atoms into the hydrocarbon is found to stabilize the material for the more severe conditions employed in exhaustive fluorination with e.g. CoF3.
~-~l~Z597 In general, in this first ~artial-fluorination stage the above-mentioned fluorinating agents may be reac-ted directly with the polycyclic hydrocarbons per se, or their partly chlorinated or brominated derivatives, if desired.
However, one exception to this is the reaction of these compounds with SF4 or dialkylaminosulfur fluorides, in which case the cyclic starting material must first be carbonylated before it can satisfactorily react with SF4 or dialkylaminosulfur fluoride. Thus, for example, in the case of the alkyladamantanes these compounds must first be converted to their corresponding ketones, aldehydes, acids, or hydroxy derivatives before they will properly react with the SF4 or dialkylaminosulfur reagent.
Illustrations of the methods for forminy these adamantyl carbonyl derivatives can be found, for example, in the teachings of U.S. Patents 3,356,740 and 3,356,741 (adamantyl ketone and diketone derivatives); U.S. Patent 3,2S0,805 (adamantyl dicarboxylic acids); U.S. Patents 3,383,424, 3,356,718, and 3,356,709 (adamantyl dihydro~ides and di-carboxylic acids). Other similar reactions will be xecognizedand understood by those skilled in the art.
Similarly, other such carbonylated pol~cyclic starting materials can be prepared in accordance with like known techniques.
It will thus be understood from the foregoing that a general recitation of the partial (i.e. first stage) fluorination of the polycyclic starting materials is in all cases intended to include their carbonyl derivatives when SF4 or dialkylaminosulfur fluorides is used as the fluorinating agent.
In addition to the use of carbonyl derivatives of cyclic materials to be perfluorinated when SF4 is used, is the use of analogous known alcohol derivatives of these compounds when HF or HF-pyridine complex is the partial fluorinating agent; and chlorinated or brominated derivatives where SbF5 is employed.
Also, cyclic dienes such as 1,3-cyclohexadiene may be reacted with fluoroolefins such as hexafluoro-propene in a Diels-Adler type reaction, to obtain partially fluorinated polycyclic hydrocarbons, as described in more detail below.
These materials may then also be perfluorinated in accordance wi~h this invention.
Thus, these aforedescribed Diels-Adler reaction products are also intended to be included in the general definition of the partially fluorinated polycyclic hydrocarbons which may then be perfluorinated with, e.g. CoF3 as described above.
It will thus be evident from the foregoing description that it is within the scope of this invention to exhaustively fluorinate a partially fluorinated, and thus stabilized, cyclic hydrocarbon regardless of how it is prepared.
The amount of fluorination necessary to impart ring structure stability to the polycyclic materials prior to their reaction with strong fluorinating agents such as CoF3 in the second and third stages of this process is not critical but desirably should comprise the replacement of from about 3-6 hydrogen atoms by fluorine atoms up to as much as a 50% replacement of such hydrogen by fluorine. The location of these fluorine atoms may be either in the nucleus or in the side chain of the hydrocarbon molecule, or both.
~2ZSg7 Accordingly, it will be understood that the product of the first stage fluorination may comprise either a single product or a mixture of partially fluorinated materials depending upon the fluorinating agent employed. This product, prior to contact with CoF3 or the like, in the next stage, should first be separated from the first fluorinating agent, preferably by distillation.
In the second stage of this process, the object is to achieve as high a degree of 1uorination as`possible short of degrading the ring structure of the compound. The effect of this fluorination step is to impart a much greater stability to the partially fluorinated polycyclic material in order that, in the last stage, virtually 100% perfluorination can be achieved under much more stringent reaction conditions without orming ring degradation by-products. This high degree of fluorination, in the second stage, which generally falls short of perfluorination by not more than S-25%, is readily accomplished by contacting the partially fluorinated hydrocarbon mixture with CoF3 in the vapor phase (by preheating) ~o at a moderate charge rate at temperatures ranging from just above the boiling point of the charge materials to about 50C above its boiling point. Preferably, a mul-ti-zone reactor with temperatures graduated from just above boiling point to 50 above should be used. Since the reaction is an exothermic one, care should be taken to control the temperature within about these ranges in order to avoid degrading the molecules.
The final stage, which likewise is in the vapor phase, comprises recycling the highly 1uorinated product of the CoF3 reaction back into the same reactor, which this
BACKGROUND OF -THE INVENTION
This invention relates to an improved process for the fluorination of polycyclic hydrocarbons. More particularly, this invention relates to an improved method for the florination, preferably perfluorination, of said hydrocarbons using a three-stage reaction which effectively eliminates the production of unwanted by-products.
U.S. Patent No. 3,6~1,167, as well as United States Patent 4,041,086 disclosure a one-staga method for making perfluoroalkyladamantanes. Recent data using new analytical techniques now show that under the reaction conditions employed therein, using CoF3 and high tempexature, degradation of the non-florinated cyclic structure does result, with the formation of ring-opened products.
SUM~RY OF THE INVENTION
In accordance with the present invention, it has now been found that polycyclic hydrocarbons may be perfluorinated with substantially no degradation o the cyclic structure by ~1) partially fluorinating the starting cyclic compound with a mild fluorinating agent under moderate conditions in a first stage, followed by (2) reacting said partially fluorinated material in a second stage in the presence of a strong fluorinating agent at temperatures just above the boiling point of said material to provide a highly fluorinated compound; and thereafter (3) recycling said highly fluorinated compound into the same second stage reactor at considerably higher temperatures to provide an essentially perfluorinated polycyclic hydrocarbon free of any degradation ring-opened products.
~ll;ZZ597 There is thus provided, in accordance with the present teachings, a process for the perfluorination of non-aromatizable polycyclic hydrocar~ons which process comprises:
a) partially fluorinating a polycyclic hydrocarbon or the carbonyl, hydroxyl, chlorinated, or brominated derivative thereof, by contacting it in a first reaction zone wi*h a fluorinating agent selected from the group consisting of HF, HF-pyridine, AgF2, MnF3, SF4, ~bF5, KCoF4 and fluoroolefins, in the liquid phase under conditions sufficient to provide not more than about 50%
fluorination corresponding to perfluorination; and b) thereafter further fluorinating the partially fluorinated polycyclic hydrocarbon in the vapor phase in a second reaction zone with CoF3 at a temperature of no greater than about 50 C~ above the boiling point of the fluorinated material to provide a highly fluorinated material having a degree of fluorination corresponding to about 75-95% of perfluorination.
As an optional step in the process, the highly fluorinated material is recovered and recycled to the second reaction zone for recontact with CoF3 in the vapor phase at a temperature about 100 higher than was first employed in step b) to provide a substantially perfluorinated polycyclic hydro-carbon.
DESCRIPTION OF THE INVENTION
-The starting materials for this improved perfluorina-tion process comprise non-aromatizable polycyclic hydrocarbons selected from the group consisting of alkyladamantanes, as des-cribed in U.S. Patent 3,6~1,167, and having from 11-30 carbon atoms, preferably 12-14 carbon atoms, such as 1~3-dimethylada-` llZZ597 mantane, 1,3,5-trimethyladam~ntane, l-ethyladamantane, l-methyl-adamantane, l-ethyl-3-methyladamantane, l-ethyl, 3,5-dimethyladamantane, or the like; endo-and exo-tetrahydro-dicyclopentadiene; methanodecalins such as 1, 4-methanodecalin or 1,4,5,8-dimethanodecalin; hydrogenated pinane; camphane;
bi-cyclooctanes; bicyclononanes; and the like. When these compounds are treated in accordance with the process of this invention, there are obtained the corresponding perfluorinated polycyclic materials in high yield and purity, wherein at least 95% of the hydrogen atoms, and more preferably 97% to ......
7 ~
~ 3a ~
~zzs9~
100%, are replaced by fluorine atoms. Generally, with this improved process, the conversion of the starting material to the corresponding perfluorinted compound is at least 50%, and most usually about 90% or more.
These perfluorin~ted materials are useful in a variety of industrial and pharmaceutical applications. The fluorinated alkyladamantanes, for example, are useful as gas turbine engine coolants, dielectric coolants for transformers, generators, and the like, as well as components in synthetic blood compositions, perfusion media, and like bi~logical applications. The perfluorinated cyclic materials are also useful as working fluids in heat pipes and Rankill cycle engines.
The first stage~of the aforedescribed process to provide a partially fluorinated intermediate is conveniently carried out by contacting the polycyclic hydrocarbon or their hydroxylated or carboxylated derivatives depending on the fluorinating agent used, in the liquid phase with a fluorinatin~ a~ent selected from the group consisting of HF, HF-pyridine complex, AgF2~ MnF3, SF4, SbF5, KCoF4, and fluoroolefins, under vary^ing conditions of temperature~
pressure, and the like, depending upon the nature of the starting material and fluorinating agent employed. These fluorinating agents are much milder in their action than CoF3 on hydrocarbons. Consequently, the degree of fluorination can be controlled by the proper selection of agent and starting material. Generally, the incorporation of from about 3 to 6 fluorine atoms into the hydrocarbon is found to stabilize the material for the more severe conditions employed in exhaustive fluorination with e.g. CoF3.
~-~l~Z597 In general, in this first ~artial-fluorination stage the above-mentioned fluorinating agents may be reac-ted directly with the polycyclic hydrocarbons per se, or their partly chlorinated or brominated derivatives, if desired.
However, one exception to this is the reaction of these compounds with SF4 or dialkylaminosulfur fluorides, in which case the cyclic starting material must first be carbonylated before it can satisfactorily react with SF4 or dialkylaminosulfur fluoride. Thus, for example, in the case of the alkyladamantanes these compounds must first be converted to their corresponding ketones, aldehydes, acids, or hydroxy derivatives before they will properly react with the SF4 or dialkylaminosulfur reagent.
Illustrations of the methods for forminy these adamantyl carbonyl derivatives can be found, for example, in the teachings of U.S. Patents 3,356,740 and 3,356,741 (adamantyl ketone and diketone derivatives); U.S. Patent 3,2S0,805 (adamantyl dicarboxylic acids); U.S. Patents 3,383,424, 3,356,718, and 3,356,709 (adamantyl dihydro~ides and di-carboxylic acids). Other similar reactions will be xecognizedand understood by those skilled in the art.
Similarly, other such carbonylated pol~cyclic starting materials can be prepared in accordance with like known techniques.
It will thus be understood from the foregoing that a general recitation of the partial (i.e. first stage) fluorination of the polycyclic starting materials is in all cases intended to include their carbonyl derivatives when SF4 or dialkylaminosulfur fluorides is used as the fluorinating agent.
In addition to the use of carbonyl derivatives of cyclic materials to be perfluorinated when SF4 is used, is the use of analogous known alcohol derivatives of these compounds when HF or HF-pyridine complex is the partial fluorinating agent; and chlorinated or brominated derivatives where SbF5 is employed.
Also, cyclic dienes such as 1,3-cyclohexadiene may be reacted with fluoroolefins such as hexafluoro-propene in a Diels-Adler type reaction, to obtain partially fluorinated polycyclic hydrocarbons, as described in more detail below.
These materials may then also be perfluorinated in accordance wi~h this invention.
Thus, these aforedescribed Diels-Adler reaction products are also intended to be included in the general definition of the partially fluorinated polycyclic hydrocarbons which may then be perfluorinated with, e.g. CoF3 as described above.
It will thus be evident from the foregoing description that it is within the scope of this invention to exhaustively fluorinate a partially fluorinated, and thus stabilized, cyclic hydrocarbon regardless of how it is prepared.
The amount of fluorination necessary to impart ring structure stability to the polycyclic materials prior to their reaction with strong fluorinating agents such as CoF3 in the second and third stages of this process is not critical but desirably should comprise the replacement of from about 3-6 hydrogen atoms by fluorine atoms up to as much as a 50% replacement of such hydrogen by fluorine. The location of these fluorine atoms may be either in the nucleus or in the side chain of the hydrocarbon molecule, or both.
~2ZSg7 Accordingly, it will be understood that the product of the first stage fluorination may comprise either a single product or a mixture of partially fluorinated materials depending upon the fluorinating agent employed. This product, prior to contact with CoF3 or the like, in the next stage, should first be separated from the first fluorinating agent, preferably by distillation.
In the second stage of this process, the object is to achieve as high a degree of 1uorination as`possible short of degrading the ring structure of the compound. The effect of this fluorination step is to impart a much greater stability to the partially fluorinated polycyclic material in order that, in the last stage, virtually 100% perfluorination can be achieved under much more stringent reaction conditions without orming ring degradation by-products. This high degree of fluorination, in the second stage, which generally falls short of perfluorination by not more than S-25%, is readily accomplished by contacting the partially fluorinated hydrocarbon mixture with CoF3 in the vapor phase (by preheating) ~o at a moderate charge rate at temperatures ranging from just above the boiling point of the charge materials to about 50C above its boiling point. Preferably, a mul-ti-zone reactor with temperatures graduated from just above boiling point to 50 above should be used. Since the reaction is an exothermic one, care should be taken to control the temperature within about these ranges in order to avoid degrading the molecules.
The final stage, which likewise is in the vapor phase, comprises recycling the highly 1uorinated product of the CoF3 reaction back into the same reactor, which this
2~9~
time is heated to a considerably higher temperature, preferably about 100C greater across the thermally graded reactor, to achieve substantially complete perfluorination, and provide yields of about 50-95%, based on the amount of original charge stock.
The perfluorinated product is then desirably cooled to temperatures of-from about 0C to-80C by passing it through several cooling traps as it is removed from the reactor in order to collect not only the product, but also HF and any other gaseous products.
The invention will now be illustrated by the following examples.
The following four examples demonstrate the preparation of partially fluorinated adamantanes which may then be perfluorinated in accordance with the process of this invention.
Adamantane dicarboxylic acid (22.4g-0.1 mole) and SF4 (27.Og-25% excess) were heated in a hoke bomb for 24 hours at 110C. The contents of the pressure vessel were cooled, extracted with CC14, filtered and the CC14 evaporated off. The residue consisted of 21.8g of bistrifluorome~
adamantane (80% yield).
ExAMæLE 2 2-adamantanone (15.0g-9.1 mole) and SF4 (13~g-25%
excess) were heated as in Example 1. The product was worked up as described in Example 1 to give 12.9g of 2,2-difluoro adamantane (75% yield).
~lZ2S97 5,7-dimethyl-1,3-adamantane dicarboxylic acid (25.2g-0.1 mole) and SF4 (27.0g-25% excess) were heated and worked up as in Example 1 to give 18g of 3,5-dimethyl-5,7-bis(trifluoromethyl) adamantane (60%).
EX~MPLE 4 .
1,3-dimethyl adamantane (42g) is added slowly to a slurry of MnF3 (1 lb) in perfluoro l-methyl decalin. After all the hydrocarbon has been added the mixture is heated with rapid stirring to 200C for 24 hours, and the Product extracted with Freon~ 113 and distilled to remove both the Freon~ 113 and perfluoro l-methyl decalin. The distillation residue consists of partially fluorinated 1,3-dimethyl adamantane in which the average molecule contains approximately 8 fluorine atoms; e.g. C12H12F8 Bistrifluoromethyl adamantane (~4cc; 33.67g;
0.123 moles) rom Example I was charged into a preheater at 0.247cc/min. The preheater temperature was 250C, and the CoF3 reactor temperature was graduated ~rom 250C in Zone 1 to 300C in Zone 4. The product line was kept at 225C.
After all the hydrocarbon had been charged to the reactor, the reactor was purged with nitrogen for 3.25 hours. The crude product weighed 46.0g. This material was water washed ~ntil the pH of the water was 5.
This material from the second stage was dried over mole sieves overnight and then 45.84g was recharged at a rate of 0.764 cc/min. to the reactor which was graduated from 275C in Zone 1 to 380C in Zone 4 for the final stage.
112ZS~7 The reactor was purged with nitrogen for 4 hours before removing the product receiver containing 47.8g. fluorocarbon;
75% material balance G.C. analysis showed the product contained 90~ perfluoro 1,3-dimethyl adamantane, confirmed by mass spectrography and FNMR.
A similar run was made with 1,3-bis(trifluoromethyl)-5, 7-dimethyl adamantane to give a 55% yield of perfluoro tetramethyl adamantane.
In a similar fashion 2,2-difluoro adamantane and 3,5-dimethyl-5,7-bis(trifluoromethyl) adamantane of Examples 2 and 3 were reacted with CoF3 in accordance with the procedures of Example 5 to give the corresponding perfluoroadamantanes in high purity and yield.
The following example illustrates the results obtained when the first (partial) fluorination stage of this invention is not employed:
Exo-tetrahydrodicyclopentadiene (25cc:24.15 g;
0.1776 moles) was charged into a preheater at 0.494 cc/min.
The preheater temperature was 225C, and the CoF3 reactor temperature was graduated from 200C in Zone 1 to 250 in Zone 4. The product line was kept at 225C. After all ~he hydrocarbon had been charged to the reactor, the reactor was purged with nitrogen for 3.25 hours. The crude product weighed 63.6 g. This material was water washed until the pH of the water was 5.
The material from the second stage was dried over mole sieves overnight and then 55.84 g was recharged at a rate of 0.764 cc/min. to the reactor which was graduated from 300C in Zone 1 to 375C in Zone 4 for the final stage.
The reactor was purged with nitrogen for 4 hours beore removing the product receiver containing 60.8 g fluorocarbon;
87~ material balance based on the 24.15 g of THDCP charged.
G.C. analysis showed the product contained 40% of endo-and exo-perfluoro-tetrahydrodicyclopentadiene, 45% of perfluoro bicyclo [3,5,0] decane and ~ 15% unknown fluorocarbons.
Exo-tetrahydrodicyclopentadiene (35 g) is added slowly to a slurry of MnF3 (1 lb) in perfluoro(l-methyl) decalin solvent. After all the hydrocarbon has been added, the mixture is heated to 200C and stirred rapidly for 24 hours. The product is extracted with Freo ~ 113 and distilled to remove both the Freon~ 113 and perfluoro (l-methyl) decalin.
The distillation residue consists of partially fluorinated tetrahydrodicyclopentadiene in which the average molecule contains approximately 7 fluorine atoms: CloH9~7.
When the thus obtained partially fluorinated te~rahydrodicyclopentadiene is then perfluroinated with CoF3 in accordance with the procedures of Example 5, there is obtained substantially pure exo-and endo-perfluorotetra-hydrodicyclopentadiene in high yield, which is essentially free of any of the by-products enumerated in Example 6.
E~AMPLE 8 In accordance with the procedures of Example 7, but substituting partially fluorinated camphane, hydrogenated pinane, 1,4-methanodecalin or 1,4,5,8-dimethanodecalin for partially fluorinated tetrahydrodicyclopentadiene, there is obtained the corresponding perfluorinated cyclocarbon in high yield, and substantially free of any deyradation ring-opened by-products.
Z~97 As indicated above, fluoroolefins and acetylenes, for example, readily undergo Diels-Alder type reactions to function as dienophiles in 1,4-cyclo-addition reactions;
their reactivity towards dienes is generally higher than that of their hydrocarbon analogues. The following examples demonstrate the preparation of partially fluorinated cyclocarbons which may then be exhaustively fluorinated in accordance with the procedures of Example 5 to provide perfluoro-cyclocarbons in high yield and essentially free of ring-opened by-products:
A. 1,3-Cyclohexadiene (1 mole) is reacted with a 25% molar excess of hexafluoropropene for 24 hours at about 150C to give 2-(trifluoromethyl) 2,3,3-trifluoro-bicyclo ~2.2.2] octane. Hydrogenation over rhodium gives 2-(tri-fluoromethyl) 2,3,3-trifluoro-bicyclo [2.2.2] octane.
B. Similarly, reaction of cyclopentadiene with hexafluoro-but-2-yne at 100C for 24 hours gives 2,3-bis (tri~
fluoromethyl) bicyclo [2.2.1] heptadiene which, upon hydro-genation over platinum, gives 2,3-bis(trifluoromethyl)bicyclo [2.2.1] heptane.
C. Also, in a like manner, octafluoro-but-2-ene and cyclopentadiene react to give 2,3-difluoro-2,3-bis(tri-fluoromethyl) bicyclo [2.2.1] heptane which, af-ter hydrogenation over ruthenium gives 2,3-bis(trifluoromethyl)bicyclo ~2.2.1 heptane.
EX~PLE 10 Norbornadiene (1 mole) and a 25% molar excess of hexafluorocyclopentadiene are heated for 24 hours at 100C to give ~ZZ5~7 ~ FFP ~
which, after treatment with CoF3 in accordance with the procedures of Example 5 yields highly pure ~erfluoro 1,4,5,8-dimethanodecalin.
time is heated to a considerably higher temperature, preferably about 100C greater across the thermally graded reactor, to achieve substantially complete perfluorination, and provide yields of about 50-95%, based on the amount of original charge stock.
The perfluorinated product is then desirably cooled to temperatures of-from about 0C to-80C by passing it through several cooling traps as it is removed from the reactor in order to collect not only the product, but also HF and any other gaseous products.
The invention will now be illustrated by the following examples.
The following four examples demonstrate the preparation of partially fluorinated adamantanes which may then be perfluorinated in accordance with the process of this invention.
Adamantane dicarboxylic acid (22.4g-0.1 mole) and SF4 (27.Og-25% excess) were heated in a hoke bomb for 24 hours at 110C. The contents of the pressure vessel were cooled, extracted with CC14, filtered and the CC14 evaporated off. The residue consisted of 21.8g of bistrifluorome~
adamantane (80% yield).
ExAMæLE 2 2-adamantanone (15.0g-9.1 mole) and SF4 (13~g-25%
excess) were heated as in Example 1. The product was worked up as described in Example 1 to give 12.9g of 2,2-difluoro adamantane (75% yield).
~lZ2S97 5,7-dimethyl-1,3-adamantane dicarboxylic acid (25.2g-0.1 mole) and SF4 (27.0g-25% excess) were heated and worked up as in Example 1 to give 18g of 3,5-dimethyl-5,7-bis(trifluoromethyl) adamantane (60%).
EX~MPLE 4 .
1,3-dimethyl adamantane (42g) is added slowly to a slurry of MnF3 (1 lb) in perfluoro l-methyl decalin. After all the hydrocarbon has been added the mixture is heated with rapid stirring to 200C for 24 hours, and the Product extracted with Freon~ 113 and distilled to remove both the Freon~ 113 and perfluoro l-methyl decalin. The distillation residue consists of partially fluorinated 1,3-dimethyl adamantane in which the average molecule contains approximately 8 fluorine atoms; e.g. C12H12F8 Bistrifluoromethyl adamantane (~4cc; 33.67g;
0.123 moles) rom Example I was charged into a preheater at 0.247cc/min. The preheater temperature was 250C, and the CoF3 reactor temperature was graduated ~rom 250C in Zone 1 to 300C in Zone 4. The product line was kept at 225C.
After all the hydrocarbon had been charged to the reactor, the reactor was purged with nitrogen for 3.25 hours. The crude product weighed 46.0g. This material was water washed ~ntil the pH of the water was 5.
This material from the second stage was dried over mole sieves overnight and then 45.84g was recharged at a rate of 0.764 cc/min. to the reactor which was graduated from 275C in Zone 1 to 380C in Zone 4 for the final stage.
112ZS~7 The reactor was purged with nitrogen for 4 hours before removing the product receiver containing 47.8g. fluorocarbon;
75% material balance G.C. analysis showed the product contained 90~ perfluoro 1,3-dimethyl adamantane, confirmed by mass spectrography and FNMR.
A similar run was made with 1,3-bis(trifluoromethyl)-5, 7-dimethyl adamantane to give a 55% yield of perfluoro tetramethyl adamantane.
In a similar fashion 2,2-difluoro adamantane and 3,5-dimethyl-5,7-bis(trifluoromethyl) adamantane of Examples 2 and 3 were reacted with CoF3 in accordance with the procedures of Example 5 to give the corresponding perfluoroadamantanes in high purity and yield.
The following example illustrates the results obtained when the first (partial) fluorination stage of this invention is not employed:
Exo-tetrahydrodicyclopentadiene (25cc:24.15 g;
0.1776 moles) was charged into a preheater at 0.494 cc/min.
The preheater temperature was 225C, and the CoF3 reactor temperature was graduated from 200C in Zone 1 to 250 in Zone 4. The product line was kept at 225C. After all ~he hydrocarbon had been charged to the reactor, the reactor was purged with nitrogen for 3.25 hours. The crude product weighed 63.6 g. This material was water washed until the pH of the water was 5.
The material from the second stage was dried over mole sieves overnight and then 55.84 g was recharged at a rate of 0.764 cc/min. to the reactor which was graduated from 300C in Zone 1 to 375C in Zone 4 for the final stage.
The reactor was purged with nitrogen for 4 hours beore removing the product receiver containing 60.8 g fluorocarbon;
87~ material balance based on the 24.15 g of THDCP charged.
G.C. analysis showed the product contained 40% of endo-and exo-perfluoro-tetrahydrodicyclopentadiene, 45% of perfluoro bicyclo [3,5,0] decane and ~ 15% unknown fluorocarbons.
Exo-tetrahydrodicyclopentadiene (35 g) is added slowly to a slurry of MnF3 (1 lb) in perfluoro(l-methyl) decalin solvent. After all the hydrocarbon has been added, the mixture is heated to 200C and stirred rapidly for 24 hours. The product is extracted with Freo ~ 113 and distilled to remove both the Freon~ 113 and perfluoro (l-methyl) decalin.
The distillation residue consists of partially fluorinated tetrahydrodicyclopentadiene in which the average molecule contains approximately 7 fluorine atoms: CloH9~7.
When the thus obtained partially fluorinated te~rahydrodicyclopentadiene is then perfluroinated with CoF3 in accordance with the procedures of Example 5, there is obtained substantially pure exo-and endo-perfluorotetra-hydrodicyclopentadiene in high yield, which is essentially free of any of the by-products enumerated in Example 6.
E~AMPLE 8 In accordance with the procedures of Example 7, but substituting partially fluorinated camphane, hydrogenated pinane, 1,4-methanodecalin or 1,4,5,8-dimethanodecalin for partially fluorinated tetrahydrodicyclopentadiene, there is obtained the corresponding perfluorinated cyclocarbon in high yield, and substantially free of any deyradation ring-opened by-products.
Z~97 As indicated above, fluoroolefins and acetylenes, for example, readily undergo Diels-Alder type reactions to function as dienophiles in 1,4-cyclo-addition reactions;
their reactivity towards dienes is generally higher than that of their hydrocarbon analogues. The following examples demonstrate the preparation of partially fluorinated cyclocarbons which may then be exhaustively fluorinated in accordance with the procedures of Example 5 to provide perfluoro-cyclocarbons in high yield and essentially free of ring-opened by-products:
A. 1,3-Cyclohexadiene (1 mole) is reacted with a 25% molar excess of hexafluoropropene for 24 hours at about 150C to give 2-(trifluoromethyl) 2,3,3-trifluoro-bicyclo ~2.2.2] octane. Hydrogenation over rhodium gives 2-(tri-fluoromethyl) 2,3,3-trifluoro-bicyclo [2.2.2] octane.
B. Similarly, reaction of cyclopentadiene with hexafluoro-but-2-yne at 100C for 24 hours gives 2,3-bis (tri~
fluoromethyl) bicyclo [2.2.1] heptadiene which, upon hydro-genation over platinum, gives 2,3-bis(trifluoromethyl)bicyclo [2.2.1] heptane.
C. Also, in a like manner, octafluoro-but-2-ene and cyclopentadiene react to give 2,3-difluoro-2,3-bis(tri-fluoromethyl) bicyclo [2.2.1] heptane which, af-ter hydrogenation over ruthenium gives 2,3-bis(trifluoromethyl)bicyclo ~2.2.1 heptane.
EX~PLE 10 Norbornadiene (1 mole) and a 25% molar excess of hexafluorocyclopentadiene are heated for 24 hours at 100C to give ~ZZ5~7 ~ FFP ~
which, after treatment with CoF3 in accordance with the procedures of Example 5 yields highly pure ~erfluoro 1,4,5,8-dimethanodecalin.
Claims (15)
1. A process for the perfluorination of non-aromatizable polycyclic hydrocarbons which comprises:
(1) partially fluorinating a polycyclic hydrocarbon by contacting it in a first reaction zone with a fluorinating agent selected from the group consisting of HF, HF-pyridine, AgF2, MnF3, SF4, SbF5; KCoF4 and fluoroolefins, in the liquid phase under conditions sufficient to provide not more than about 50% fluorination corresponding to perfluorination;
(2) thereafter further fluorinating said partially fluorinated polycyclic hydrocarbon in the vapor phase in a second reaction zone with CoF3 at a temperature of no greater than about 50°C above the boiling point of the fluorinated material to provide a highly fluorinated material having a degree of fluorination corresponding to no more than about 75-95% of perfluorination; and (3) recovering and recycling said highly fluorinated material to said second reaction zone and recontacting the same with CoF3 in the vapor phase at temperatures about 100°C higher than were first employed in (2) above, to provide a substantially perfluorinated polycyclic hydrocarbon.
(1) partially fluorinating a polycyclic hydrocarbon by contacting it in a first reaction zone with a fluorinating agent selected from the group consisting of HF, HF-pyridine, AgF2, MnF3, SF4, SbF5; KCoF4 and fluoroolefins, in the liquid phase under conditions sufficient to provide not more than about 50% fluorination corresponding to perfluorination;
(2) thereafter further fluorinating said partially fluorinated polycyclic hydrocarbon in the vapor phase in a second reaction zone with CoF3 at a temperature of no greater than about 50°C above the boiling point of the fluorinated material to provide a highly fluorinated material having a degree of fluorination corresponding to no more than about 75-95% of perfluorination; and (3) recovering and recycling said highly fluorinated material to said second reaction zone and recontacting the same with CoF3 in the vapor phase at temperatures about 100°C higher than were first employed in (2) above, to provide a substantially perfluorinated polycyclic hydrocarbon.
2. The process according to Claim 1 wherein the temperature in the first reaction zone ranges from about 175 to 350°C.
3. The process according to Claim 1 wherein the temperatures in step (2) are graduated from just above the boiling point of the recycled materal in the first part of the second reaction zone to about 50°C above said boiling point in the last part of said reaction zone.
4. The process according to Claim 1 wherein the temperatures in step (3) are graduated from about 100°C
above the boiling point of the recycled material in the first part of said second reaction zone to about 150°C above said boiling point in the last part of said reaction zone.
above the boiling point of the recycled material in the first part of said second reaction zone to about 150°C above said boiling point in the last part of said reaction zone.
5. The process according to Claim 1 wherein the polycyclic hydrocarbon is an alkyladamantane having from 11 to 30 carbon atoms.
6. The process according to Claim 5 wherein the fluorinating agent in the first reaction zone is SF4 and the alkyladamantane is in the form of a carbonylated derivative thereof.
7. The process according to Claim 5 wherein the alkyladamantane, 1-ethyladamantane, 1-methyladamantane, 1-ethyl-3-methyladamantane, or 1-ethyl-3,5-dimethyladamantane.
8. The process according to Claim 1 wherein the polycyclic hydrocarbon is exo-or-endotetrehydrodicyclo-pentadiene.
9. The process according to Claim 1 wherein the polycyclic hydrocarbon is bicyclooctane or bicyclononane.
10. The process according to Claim 1 wherein the polycyclic hydrocarbon is a methanodecalin.
11. The process for the perfluorination of non-aromatizable polycyclic hydrocarbons which comprises:
(A) partially fluorinating a polycyclic hydrocarbon or the carbonyl, hydroxyl, chlorinated or brominated derivative thereof, by contacting it in a first reaction zone with a fluorinating agent selected from the group consisting of HF, HF-pyridine, AgF2, MnF3, SF4, SbF5, KCoF4 and fluoroolefins, in the liquid phase under conditions sufficient to provide not more than about 50% fluorination corresponding to perfluorination; and (B) thereafter further fluorinating said partially fluorinated polycyclic hydrocarbon in the vapor phase in a second reaction zone with CoF3 at a temperature of no greater than about 50°C. above the boiling point of the fluorinated material to provide a highly fluorinated material having a degree of fluorination corresponding to about 75-95% of perfluorination.
(A) partially fluorinating a polycyclic hydrocarbon or the carbonyl, hydroxyl, chlorinated or brominated derivative thereof, by contacting it in a first reaction zone with a fluorinating agent selected from the group consisting of HF, HF-pyridine, AgF2, MnF3, SF4, SbF5, KCoF4 and fluoroolefins, in the liquid phase under conditions sufficient to provide not more than about 50% fluorination corresponding to perfluorination; and (B) thereafter further fluorinating said partially fluorinated polycyclic hydrocarbon in the vapor phase in a second reaction zone with CoF3 at a temperature of no greater than about 50°C. above the boiling point of the fluorinated material to provide a highly fluorinated material having a degree of fluorination corresponding to about 75-95% of perfluorination.
12. The process according to claim 11 wherein the temperature in the first reaction zone ranges from about 175° to 350°C.
13. The process according to claim 11 wherein the temperature in step (B) is graduated from just above the boiling point of the recycled material in the first part of the second reaction zone to about 50°C. above said boiling point in the last part of said reaction zone.
14. The process according to claim 11 wherein the polycyclic hydrocarbon is an alkyladamantane having from 11 to 30 carbon atoms.
15. The process according to claim 14 wherein the fluorinating agent in the first reaction zone is SF4 and the alkyladamantane is in the form of a carbonylated derivative thereof.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA380,858A CA1129411A (en) | 1977-02-25 | 1981-06-29 | Cyclic hydrocarbon perfluorination process |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US77187377A | 1977-02-25 | 1977-02-25 | |
| US771,873 | 1977-02-25 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1122597A true CA1122597A (en) | 1982-04-27 |
Family
ID=25093219
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA297,549A Expired CA1122597A (en) | 1977-02-25 | 1978-02-23 | Cyclic hydrocarbon perfluorination process |
Country Status (13)
| Country | Link |
|---|---|
| JP (1) | JPS53116359A (en) |
| BE (1) | BE864328A (en) |
| CA (1) | CA1122597A (en) |
| CH (1) | CH637910A5 (en) |
| DE (1) | DE2808112A1 (en) |
| DK (1) | DK84878A (en) |
| FI (1) | FI69831C (en) |
| FR (1) | FR2381732A1 (en) |
| GB (1) | GB1597914A (en) |
| IT (1) | IT1095441B (en) |
| NL (1) | NL7802145A (en) |
| NO (2) | NO153607C (en) |
| SE (2) | SE428206B (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5821628A (en) * | 1981-07-29 | 1983-02-08 | Dainippon Ink & Chem Inc | Norbornadiene derivative and its preparation |
| US4929317A (en) * | 1986-12-01 | 1990-05-29 | Tokuyama Soda Kabushiki Kaisha | Process for preparation of perfluoro organic compounds |
| JP2010215524A (en) * | 2009-03-13 | 2010-09-30 | Fujifilm Corp | Fluorobicyclo[2.2.2]octane compound, method for producing the same, and use thereof |
| JP2010215523A (en) * | 2009-03-13 | 2010-09-30 | Fujifilm Corp | Fluorobicyclo[2.2.2]-2-octene compound, method for producing the same, and use thereof |
| RU2451006C1 (en) * | 2011-05-05 | 2012-05-20 | Общество с ограниченной ответственностью "ГалоПолимер Кирово-Чепецк" (ООО "ГалоПолимер Кирово-Чепецк") | Method of producing perfluorocycloalkanes |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3641167A (en) * | 1965-03-17 | 1972-02-08 | Sun Oil Co | Highly fluorinated alkyladamantanes |
| US4041086A (en) * | 1972-02-07 | 1977-08-09 | Sun Ventures, Inc. | Process of manufacture of flourinated alkyladamantanes |
-
1978
- 1978-02-23 FI FI780610A patent/FI69831C/en not_active IP Right Cessation
- 1978-02-23 CA CA297,549A patent/CA1122597A/en not_active Expired
- 1978-02-24 DE DE19782808112 patent/DE2808112A1/en active Granted
- 1978-02-24 SE SE7802153A patent/SE428206B/en not_active IP Right Cessation
- 1978-02-24 CH CH205178A patent/CH637910A5/en not_active IP Right Cessation
- 1978-02-24 IT IT20651/78A patent/IT1095441B/en active
- 1978-02-24 DK DK84878A patent/DK84878A/en not_active Application Discontinuation
- 1978-02-24 NO NO780651A patent/NO153607C/en unknown
- 1978-02-25 JP JP2041278A patent/JPS53116359A/en active Granted
- 1978-02-27 BE BE185487A patent/BE864328A/en not_active IP Right Cessation
- 1978-02-27 FR FR7805528A patent/FR2381732A1/en active Granted
- 1978-02-27 GB GB7727/78A patent/GB1597914A/en not_active Expired
- 1978-02-27 NL NL7802145A patent/NL7802145A/en not_active Application Discontinuation
-
1981
- 1981-05-07 SE SE8102878A patent/SE448371B/en not_active IP Right Cessation
-
1984
- 1984-03-28 NO NO841238A patent/NO153965C/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| FI69831C (en) | 1986-05-26 |
| GB1597914A (en) | 1981-09-16 |
| FI69831B (en) | 1985-12-31 |
| IT1095441B (en) | 1985-08-10 |
| JPS6254088B2 (en) | 1987-11-13 |
| BE864328A (en) | 1978-08-28 |
| NO153965B (en) | 1986-03-17 |
| NO153607C (en) | 1986-04-23 |
| NO780651L (en) | 1978-08-28 |
| SE448371B (en) | 1987-02-16 |
| CH637910A5 (en) | 1983-08-31 |
| JPS53116359A (en) | 1978-10-11 |
| SE8102878L (en) | 1981-05-07 |
| NO153607B (en) | 1986-01-13 |
| IT7820651A0 (en) | 1978-02-24 |
| FR2381732B1 (en) | 1983-11-25 |
| NO153965C (en) | 1986-06-25 |
| DE2808112A1 (en) | 1978-08-31 |
| DK84878A (en) | 1978-08-26 |
| FI780610A (en) | 1978-08-26 |
| SE428206B (en) | 1983-06-13 |
| NO841238L (en) | 1978-08-28 |
| DE2808112C2 (en) | 1989-04-27 |
| SE7802153L (en) | 1978-08-26 |
| FR2381732A1 (en) | 1978-09-22 |
| NL7802145A (en) | 1978-08-29 |
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