FI69831B - FOERFARANDE FOER PERFLUORERING AV ICKE-AROMATISERBARA POLYCYCLISKA KOLVAETEN - Google Patents

Description

_ .... PATENT PUBLICATION / Q07> ^ (11) PATENTSKRIFT 0 ^ 0 0Ί SS # (51) Kv.lkt / Int.Cli * C 07 C 23/20, 17/10 (21) Patent application - Patentansöknlng 780610 ¢ 22) Application date - Ansöknlngsdag 23.02.78 (23 ) Starting date - Giltlghetsdag 23 02 78 FINLAND-FINLAND (41) Made public - Blivlc offentlig 26.08.78

/ c. \ (44) Date of dispatch and of publication. “Q

(*) Ansttkan utlagd och utl.skrlften publicerad * '· 1 4.85 (45) Patenttf granted - Patent meddelat 26.05.86

National Board of Patents and Registration (86) International application - lnt.ansökan

Patent-och registerstyrelsen (32) (33) (31) Claim claimed - Begärd prloritet 25.02.77 USA (US) 771873 (73) Adamantech, Inc., Second and Green Streets (P.O. Box 1195),

Marcus Hook, PA, USA (72) Robert Emory Moore, Wilmington, Delaware, USA (7) Berggren Oy Ab (5 * 0 Process for the perfluorination of unflavoured polycyclic hydrocarbons - Förfarande för perffuorering av icke- aromatiserbara polycyk-1iska moths

The present invention relates to an improved process for fluorinating polycyclic hydrocarbons. More specifically, the invention relates to an improved process for carrying out fluorination, preferably per-fluorination, using said hydrocarbons and a three-step reaction which effectively eliminates the formation of harmful by-products.

U.S. Patent 3,641,167 discloses a one-step process for preparing perfluoroalkyl adamantanes. Using new analytical techniques, it has now been shown that under the reaction conditions used and with the use of CoF3 and high temperature, no decomposition of the non-fluorinated cyclic structure and formation of open-ring products occurs.

In accordance with the present invention, it has now been found that polycyclic hydrocarbons can be perfluorinated without substantially any degradation of the cyclic structure. The process of the invention is characterized in that (1) the polycyclic hydrocarbon is partially fluorinated by contacting it in the first reaction zone with a fluorinating agent selected from the group consisting of HF, HF-pyridine, AgF2, MnF2 / SF2, SbF1. , KCoF4 and fluoroolefins, under liquid phase conditions that provide up to about 50% fluorination equivalent to perfluorination, (2) the partially fluorinated polycyclic hydrocarbon is then further fluorinated in the second reaction zone in the gas phase at a temperature of up to about 50 ° C with fluorine. above the boiling point to obtain a highly fluorinated product having a fluorination degree of up to about 75-95% perfluorination, and (3) said highly fluorinated product is reacted with CoF 4 in the gas phase at a temperature about 100 ° C higher than the temperature first used in (2) above, a substantially perfluorinated polys to form a monohydrocarbon.

The starting materials for this improved perfluorination process are non-aromatic polycyclic hydrocarbons selected from the group consisting of alkyl adamantanes, as described in U.S. Patent No. 3,641,167, having from 11 to 30 carbon atoms, preferably from 12 to 14 carbon atoms, and e.g. 1,3-dimethyladamantane, 1,3,5-trimethyladamantane, 1-ethyladamantane, 1-methyladamantane, 1-ethyl-3-methyladamantane, 1-ethyl-3,5-dimethyladamantane and the like, endo- and exo-tetrahydrodicyclopentadiene , methanodecalins such as 1-4-methanodecalin or 1,4,5,8-dimethanodecalin, hydrogenated pinane, camphane, bicyclooctanes, bicyclononanes, etc. By treating these compounds according to the invention, the corresponding perfluorinated polycyclic materials are obtained in high yield and purity. wherein at least 95% of the hydrogen atoms and more preferably 97-100% of them have been replaced by fluorine atoms. Using this improved process, the conversion of starting materials to the corresponding perfluorinated compounds is generally at least 50% and most usually about 90% or greater.

Il 3 69831 These perfluorinated products are useful in a variety of industrial and pharmaceutical applications. For example, fluorinated alkyl adamantanes are useful refrigerants for gas turbine equipment, electrically insulating refrigerants for transformers, generators, and the like, as well as ingredients for synthetic blood compositions, perfusion media, and other biological products. Perfluorinated cyclic products are also useful processing fluids in heating tubes and Rankin rotary motors.

The first step in the process described above for the preparation of a partially fluorinated intermediate is suitably carried out by contacting 4,69831 polycyclic hydrocarbons or their hydroxylated or carboxylated derivative depending on the fluorinating agent used in the liquid phase with a fluorinating agent selected from the group consisting of HF, HF-F , SbF 2, KCOF 4 and fluoroolefins at various temperatures, pressures and the like. conditions depending on the nature of the starting material and the fluorinating agent used. These fluorinating agents are much more gentle in their action than C0F3 hydrocarbons. Thus, the degree of fluorination can be adjusted by appropriately selecting the treatment agent and the starting material. In general, the incorporation of about 3 to 6 fluorine atoms into a hydrocarbon has been found to stabilize this material for the more severe conditions used in the final fluorination, e.g., with CoF3.

In this first partial fluorination step, the above-mentioned fluorinating agents can generally be reacted directly with polycyclic hydrocarbons per se or, if desired, with their partially chlorinated or brominated derivatives. An exception to this is, however, the reaction of these compounds with SF / pn or dialkylamino sulfur fluoride, in which case the cyclic starting materials must first be carbonylated before they can be satisfactorily reacted with SF4 or dialkylamino sulfur fluoride. Thus, for example, in the case of alkyl adamantanes, these compounds must first be converted into the corresponding ketones, aldehydes, acids or hydroxy derivatives before they can be reacted with SF4 or a dialkylamino sulfur reagent.

Methods for forming these adamantyl carbonyl derivatives are described, for example, in U.S. Patent Nos. 3,356,740 and 3,356,741 (adamantyl ketone and diketone derivatives), U.S. Patent Nos. 3,250,805 (adamantyl dicarboxylic acids), U.S. Patent No. 3,406,246, adamantyl dihydroxides and dicarboxylic acids). One skilled in the art can list other similar reactions.

Other such carbonylated polycyclic starting materials can also be prepared in a known manner.

It is therefore to be understood from the above that the reference to the partial (first stage) fluorination of polycyclic

II

69831 also refers to their carbonyl derivatives when SF 4 or dialkylamino sulfur fluorides are used as the fluorinating agent.

In addition to the use of carbonyl derivatives of fluorinated cyclic materials, analogous known alcohol derivatives of these compounds can be used when SF4 is used when the HF or HF-pyridine complex is a partial fluorinating agent and chlorinated and brominated derivatives when the reagent used is SbF2.

Cyclic dienes such as 1,3-cyclohexadiene can also be used to react with fluoroolefins such as hexafluoropropylene in a Diels-Adler-type reaction to obtain partially fluorinated polycyclic hydrocarbons as described in more detail below. These products can then be perfluorinated according to the invention.

Thus, these Diels-Adler reaction products described above are also intended to be included in the general definition of partially fluorinated polycyclic hydrocarbons and can then be perfluorinated using e.g. CoF 2 as described above.

It is thus apparent from the foregoing description that it is within the scope of the invention to thoroughly fluorinate a partially fluorinated and thus stabilized cyclic hydrocarbon, regardless of how it is prepared.

The amount of fluorination necessary to provide ring structure stability to the polycyclic products prior to their reaction with strong fluorinating agents such as CoF3 in the second and third treatment steps is not critical, but preferably involves replacing 3 to 6 hydrogen atoms with fluorine atoms until about 50% of these hydrogen atoms have been replaced by fluorine. These fluorine atoms may be located either in the ring or in the side chain of the hydrocarbon molecule, or both. Thus, it will be appreciated that the fluorination product of the first stage may be either a single product or a mixture of partially fluorinated products, depending on the fluorinating agent used. This product must first be separated from the fluorination agent of the first stage, preferably by distillation, in the next step before contact with CoF3 or the like.

The purpose of the second step of this treatment is to obtain the highest possible degree of fluorination without damaging the ring structure of the compound. This fluorination step provides much greater stability to the partially fluorinated polycyclic material with the intention that in the last step 100% perfluorination can be achieved under much more intense reaction conditions without the formation of ring-decomposed by-products. This high degree of fluorination in the second stage, where perfluorination generally does not exceed 5-25%, is readily accomplished by contacting the partially fluorinated hydrocarbon mixture with CoF3 in the atmosphere (preheating) using a reasonable feed rate at a temperature ranging from about 50 ° C above the boiling point of the feedstock. . In this case, a reactor with several zones is preferably used, in which the temperature gradually rises from the boiling point to a value of about 50 ° above it. Because the reaction is exothermic, care must be taken to control the temperature within these limits to prevent molecular degradation.

The final step, which also takes place in the gas phase, involves returning the highly fluorinated product from the CO 3 reaction to the same reactor, which is currently heated to a much higher temperature, preferably about 100 ° C, in a reactor where the temperature gradually rises to provide substantially complete perfluorination and about 50-95% yield based on the original raw material.

The perfluorinated product is then preferably cooled to a temperature of about 0-80 ° C by passing it through several cooling steps after its removal from the reactor in order to recover not only the product but also the HF and all other gaseous products.

The invention is illustrated by the following examples.

The following four examples illustrate the preparation of partially fluorinated adamantanes, which can then be perfluorinated using the process of the invention.

Example 1

Adamantanedicarboxylic acid (22.4 g; 0.1 mol) and SF 4 (27.0 g; 25% excess) were heated in a pressure vessel at 110 ° C for 24 h.

The contents of the pressure vessel were cooled, extracted with CCl 4, filtered and the CCl 4 evaporated. The residue contained 21.8 g of bistrifluoromethyladamantane (yield 80%).

69831

Example 2 2-Adamantanone (15.0 g; 9.1 moles) and SF 4 (13.0 g; 25% excess) were heated as described in Example 1. The product was treated as described in Example 1 to give 12.9 g of 2,2-difluoroadamantane (75% yield).

Example 3 5,7-Dimethyl-1,3-adamantanedicarboxylic acid (25.2 g; 0.1 mol) and SF 4 (27.0 g; 25% excess) were heated and treated according to Example 1 to give 18 g of 3.5 -dimethyl-5,7-bis (trifluoromethyl) adamantane (60%).

Example 4 1,3-Dimethyladamantane (42 g) is slowly added to a slurry of MnF 4 (454 g) in perfluoro-1-methyldecalin. After all the hydrocarbon has been added, the mixture is heated to 200 ° C with rapid stirring for 24 hours and extracted with "Freon 113" and distilled to remove both "Freon 113" and perfluoro-1-methyl-decalin. The distillation residue consists of partially fluorinated 1,3-dimethyladamantane with an average of 8 fluorine atoms in the molecule, e.g. ci2H12F8 *

Example 5

The bistrifluoromethyladamantane from Example 1 (24 ml; 33.67 g; 0.123 mol) was introduced into the preheater at a rate of 0.247 ml / min. The preheater temperature was 250 ° C and the temperature of the CoF3 reactor changed from 250 ° C in zone 1 to 300 ° C in zone 4. The product supply line temperature was maintained at 225 ° C. After all the hydrocarbon had been introduced into the reactor, the reactor was purged with nitrogen for 3 1/4 hours. The weight of the crude product was 46.0 g. This material was washed with water until the pH of the water was 5.

This second-stage material was dried overnight on molecular sieves and then re-introduced at a rate of 45.84 g at 0.764 ml / min into a reactor at 275 ° C in zone 1 and 380 ° C in zone 4 at 69831 δ. last step. The reactor was purged with nitrogen for 4 h before removing the product collection vessel containing 47.8 g of fluorocarbon. 75% G.C. analysis of the product showed that the product contained 90% perfluoro-1,3-dimethyladamantane, which could be confirmed by mass spectrometry and FNMR.

A similar experiment was performed using 1,3-bis (trifluoromethyl) -5,7-dimethyladamantane to give perfluorotetramethyladamantane in 55% yield.

In a similar manner, 2,2-difluoroadamantane and 3,5-dimethyl-5,7-bis (trifluoromethyl) adamantane from Examples 2 and 3 were reacted with CoF3 according to Example 5 to give the corresponding perfluoroadamantenes of good purity. in high yield.

Example 6

The following example illustrates the results obtained when the first (partial) fluorination step according to the invention is not used.

Exo-tetrahydrodicyclopentadiene (25 mL; 24.15 g; 0.1776 moles) was introduced into the preheater at a rate of 0.494 mL / min. The preheating temperature was 225 ° C and the temperature of the CoF 3 reactor increased from the value of zone 1 at 200 ° C to the value of zone 4 at 250 ° C. The product supply line was maintained at 225 ° C. After all the hydrocarbon had been introduced into the reaction vessel, it was purged with nitrogen within 3.25 hours. The weight of the crude product was 63.6 g. This product was washed with water until the pH of the water was 5.

The product from the second step was dried through molecular sieves overnight and then 55.84 g was recirculated at a rate of 0.764 ml / min to a reactor whose temperature rose from zone 1 in 30 ° C to 375 ° C in the last zone 4. The reactor was purged with nitrogen for 4 h before removing the product receiving vessel containing 60.8 g of fluorocarbon. The equilibrium value of the product was 87% using 24.15 g and the THDCP test. G.C. analysis showed the product to contain 40% endo- and exo-perfluoro-tetrahydrodicyclopentadiene, 45% perfluorobicyclo [3.5.7] decane and about 15% unknown fluorocarbons.

9 69831

Example 7

Exo-tetrahydrodicyclopentadiene (35 g) is slowly added to a slurry of MnF 4 (454 g) in perfluoro (1-methyl) decalin solvent. After all the hydrocarbon has been added, the mixture is heated to 200 ° C and stirred rapidly for 24 h. The mixture thus obtained is extracted with "Freon 113" and distilled to remove both "Freon 113" and perfluoro- (1-methyl) decalin. The distillation residue consists of partially fluorinated tetrahydrodicyclopentadiene having an average molecular weight of about 7 fluorine atoms: C

When the partially fluorinated tetrahydrodicyclopentadiene thus obtained is then perfluorinated with CoF3 according to Example 5, substantially pure exo- and endo-perfluorotetrahydrodicyclopentadiene is obtained in good yield and is substantially free of all the by-products mentioned in Example 6.

Example 8

Carrying out the treatment according to Example 7, but using partially fluorinated camphane, hydrogenated pinane, 1,4-methanodecalin or 1,4,5,8-dimethanodecalin instead of partially fluorinated tetrahydrodicyclopentadiene, gives the corresponding perfluorinated cyclic hydrocarbon in high yield and is substantially free of broken ring-opened products.

Example 9

As mentioned above, fluoroolefins and acetylenes readily undergo, for example, a Diels-Adler-type reaction to form dienophiles in 1,4-cyclo addition reactions. Their tendency to react to dienes is generally greater than that of their hydrocarbon analogs. The following examples illustrate the preparation of partially fluorinated hydrocarbons which can then be strongly fluorinated by the process of Example 5 to give perfluorocyclocarbons in high yield and are substantially free of open ring by-products.

A. 1,3-Cyclohexadiene (1 mole) is reacted with a 25 mole excess of hexafluoropropene for 24 h at about 150 ° C to give 2- (trifluoromethyl) -2,3,3-trifluoro-bicyclo / 2.2.2 / octane. Hydrogenation with rhodium gives 2- (trifluoromethyl) -2,3,3-trifluoro-bicyclo / 2,2,27-octane.

1 o 69831 B. In a similar manner, the reaction of cyclopentadiene with hexafluorobut-2-yne at 100 ° C for 24 hours gives 2,3-bis (trifluoromethyl) bicyclo [2.2.1] heptadiene, which after hydrogenation is obtained with platinum. 2,3-bis (trifluoromethyl) bicyclo [2.2.1] heptane.

C. Octafluoro-but-2-ene and cyclopentadiene react in a similar manner to give 2,3-difluoro-2,3-bis (trifluoromethyl) -bicyclo [2.2.1] heptane, which after hydrogenation forms a ruthenium 2,3-bis (trifluoromethyl) bicyclo [2.2.1] heptane.

Example 10

Norbornadiene (1 mole) and 25% molar excess of hexafluorocyclopentadiene are heated at 100 ° C for 24 h to give compound

F F

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F

from which, after treatment with CoF3 using the method of Example 5, highly pure perfluoro-1,4,5,8-dimethanedecalin is obtained.

Claims (11)

A process for perfluorinating non-aromatizable polycyclic hydrocarbons using CoF 2 as a fluorinating agent, characterized in that (1) the polycyclic hydrocarbon is partially fluorinated by contacting it in a first reaction zone with a fluorinating agent selected from the group formed by HF, HF-pyridine, A9F2 'MnF3 · SF4 · SbF,., KCoF4, and fluorolefins, in liquid phase under conditions providing a fluorination corresponding to a maximum of 50% perfluorination, (2) then further fluorinated. the partially fluorinated polycyclic hydrocarbon in a second gas phase reaction zone with CoF 3 at a temperature not exceeding about 50 ° C above the boiling point of the fluorinated material to obtain a highly fluorinated product having a fluorination degree corresponding to no more than about 75-95% perfluorination and (3) said highly fluorinated product is reacted with CoF 2 in gas phase at a temperature of about 100 ° C above the temperature first used in point (2) above to form a late perfluorinated polycyclic hydrocarbon. 2. A method according to claim 1, characterized in that the product obtained in step (3) from the second zone is circulated back to the second stage. 3. A process according to claim 1, characterized in that the temperature of the first reaction zone is about 17-5-350 ° C. 4. A method according to claim 1, characterized in that the temperatures in step (2) are controlled from a value which is just above the boiling point of the ether circulated material in the first part of the second reaction zone, to about 50 ° C above said boiling point. the last part of the reaction zone.