SE428206B - PROCEDURE FOR PERFLUORING THE NON-AROMATIZABLE POLYCYCLIC CULVET - Google Patents

Description

1-ethyl-S-methyl adamantane, various industrial and pharmaceutical applications. fluorination is followed by a gas phase reaction carried out in a second step with a fluoride of cobalt at temperatures which are usually immediately above the boiling point of the material, to form highly fluorinated cyclic compounds, followed by a reaction in a third step with the same reagent as in step two but at significantly higher temperatures, to form the desired perfluorinated material. Alternatively, the partially fluorinated material used in the second step may be derived from known sources using any known partially fluorinated cyclic hydrocarbon. The starting materials for this improved perfluorination process include non-aromatizable polycyclic hydrocarbons selected from the group consisting of alkyl adamantanes, as described in U.S. Pat. No. 3,641,167, and having 11 to 30 carbon atoms, preferably 12 to 14 carbon atoms, such as 1, 3-dimethyl adamantane, 1,3,5-trimethyl adamantane, 1-ethyl adamantane, 1-methyl adamantane, 1-ethyl-3,5-dimethyl adamantane or the like; endo- and exo-tetrahydrodicyclopentadiene; methanodecalines such as 1,4-methanodecalin or 1,4,5,8-dimethanodecalines; hydrated pine; kamfan; bicyclooctanes; bicyclononanes; and similar.

When these compounds are treated according to the process of the present invention, the corresponding perfluorinated polycyclic materials are obtained in high yield and with high purity, at least 95% of the hydrogen atoms, and more preferably 97-100%, being replaced by fluorine atoms. more.

These perfluorinated materials are useful in a variety of The fluorinated alkyl diamantanes e.g. are useful as coolants for gas turbine engines, dielectric coolants for transformers, generators and the like, as well as components in synthetic blood compositions, perfusion media and similar biological applications. The perfluorinated cyclic materials are also useful as working fluids in heat pipes and Rankín bicycle engines.

The first step in the process described above, in which step a partially fluorinated intermediate is obtained, is conveniently carried out by bringing the polycyclic hydrocarbon. In this process, the conversion of the starting material to the corresponding taper-fluorinated compound is improved. is at least 50% and usually about 90% or the hydroxylated or carboxylated derivative thereof, depending on the fluorinating agent used, in liquid phase contact with a fluorinating agent selected from the group consisting of MnF , SF4, KCOF4 and fluorolefins under varying conditions in terms of temperature, pressure and the like, depending on the starting material used and the fluorinating agent used. These fluorinating agents are much milder in their action than CoF3 on hydrocarbons. Consequently, the degree of fluorination can be regulated by appropriate selection of agents and starting materials. In general, the incorporation of from about 3 to 6 fluorine atoms into the hydrocarbon has been found to stabilize the material for the more difficult conditions used in exhaustive fluorination with e.g. CoF3.

Usually, in this first step of partial fluorination, the above-mentioned fluorinating agents can be reacted directly with the polycyclic hydrocarbons themselves, or their partially chlorinated or brominated derivatives, if desired. An exception to this, however, is the reaction of these compounds with SF4 or dialkylamino sulfur fluorides, in which case the cyclic starting material must first be carbonylated before it can react satisfactorily with SF4 or dialkylaminosulfur fluoride. In the case of alkyl adamantanes, e.g. these compounds are first converted to the corresponding ketones, aldehydes, acids or hydroxide derivatives, before they can react satisfactorily with the SF4 or dialkylamino sulfur reagent.

Examples of methods for preparing these adamantyl carbonyl derivatives are e.g. U.S. Pat. Nos. 3,356,740 and 3,356,741 (adamantyl ketone and diketone derivatives; U.S. Pat. No. 3,250,805 (adamantyldicarboxylic acids]; U.S. Patents 3,383,424, 3,356,718 and 5,356,709 be obvious and understood by those skilled in the art.

Similarly, other such carbonylated polycyclic starting materials can be prepared according to similar prior art.

From the above it thus appears that, when the partial fluorination (ie in the first step) of the polycyclic starting materials is generally mentioned, this fluorination is in all cases intended to include the carbonyl derivatives of the materials when SF4 or dialkylaminosulfur fluorides are used as fluorinating agents. In addition, cyclic dienes, such as 1,3-cyclohexadiene, can also be reacted with fluorolefins, such as hexafluoropropylene, in a Diels-Alder type reaction, to provide of partially fluorinated polycyclic hydrocarbons, which will be described in more detail below. These materials can then also be perfluorinated in accordance with the present invention. The Diels-Alder reaction products mentioned above are thus also intended to be included in the general definition of the partially fluorinated polycyclic hydrocarbons, which can then be perfluorinated with e.g. COF3 as described above. It is thus clear from the above description that it is within the scope of the invention to exhaustively or extensively fluorinate a partially fluorinated, and thus stabilized cyclic, hydrocarbon regardless of how it is prepared.

The degree of fluorination necessary to impart ring structure stability to the polycyclic materials before they are reacted with strong fluorinating agents, such as CoF 3, in the second and third steps of the present process is not critical, but preferably it should involve a yield of about 3 -6 hydrogen atoms with fluorine atoms up to as much as a 50% yield of such hydrogen to fluorine. The location of these fluorine atoms can be either in the nucleus or in the side chain of the hydrocarbon molecule, or both. Accordingly, it is understood that the product from the fluorination in the first step may be either a single product or a mixture of partially fluorinated material depending on the fluorinating agent used. This product should, before being brought into contact with CoF3 or the like, in the subsequent step, first be separated from the first fluorinating agent, preferably by distillation.

In the second step of the process, the aim is to achieve as high a degree of fluorination as possible without destroying or degrading the ring structure of the compound. The effect of this fluorination step is to impart greater stability to the partially fluorinated polycyclic material so that in the last step one can achieve practically 100% perfluorination under much stronger or more drastic reaction conditions without the formation of ring degradation by-products. This high degree of fluorination, in the second stage, which usually falls outside perfluorination by no more than 5-25%, is easily accomplished by bringing the partially fluorinated hydrocarbon mixture in contact with CoF3 in the vapor phase (by preheating) at a moderate rate of charge and at a temperature ranging from immediately above the boiling point of the charge materials to about 50 ° C above their boiling point. Preferably, a multi-zone reactor is used, where the temperatures vary from just above the boiling point to 500 above. Since the reaction is exothermic, care should be taken to regulate the temperature within approximately these limits in order to avoid degradation of the molecules.

The last step, which also takes place in the vapor phase, involves recycling the highly fluorinated product from the CoF3 reaction back into the same reactor, which this time is heated to a considerably higher temperature, preferably about 100 ° C higher above the thermally graded reactor. , for achieving substantially complete perfluorination and for achieving yields of about 50-95%, calculated on the amount of raw material originally invested.

The perfluorinated product is then suitably cooled to a temperature of from about 0 ° C to 80 ° C by passing it through a plurality of cooling traps, when removed from the reactor, in order to collect not only the product but also HF and possibly other gaseous products.

The invention will now be illustrated by the following examples.

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

EXAMPLE 1 Adamantane dicarboxylic acid (22.4 g-0.1 mol) and SF4 (27.0 g - 25% excess) were heated in a pressure bomb for 24 hours at 10 ° C.

The contents of the pressure vessel were cooled, extracted with CCl 4 and filtered, and CCl 4 was evaporated. The residue consisted of 21.8 g of bistrifluoromethyl adamantane (80% yield); kp. 71 ° C at 10 mm Hg.

EXAMPLE 2 5,7-Dimethyl-1,3-adamantane dicarboxylic acid (25.2 g-0.1 mol) and SF4 (27.0 g-25% excess) were heated and worked up as in Example 1 to give 18 g 3,5-dimethyl-5,7-bis (trifluoromethyl) adamantane (60%); kp. 80-83 ° C at 0.5 mm Hg; m.p. 58 ° C- 41802153-2 10 15 20 25 30 35 'value was 5.' zzs ° c, pch cor BXÉMPBL 3 _p 1,3-dimethyl adamantane (42 g) was slowly added to a slurry of MnF 3 (0.45 kg) in perfluoro-1-methyldecalin. After. addition of all hydrocarbon, the mixture was heated with rapid stirring to Z00 ° C for 24 hours, and the product was extracted with "Freon 113" and distilled to remove both "Freon 13" and perfluoro-1-methyldecalin. The distillation residue consisted of partially fluorinated 1,3-dimethyl adamantane, wherein the average molecule contains approximately 8 fluorine atoms, e.g. çlznlzrs, and which boils at 215-150 ° C.

EXAMPLE 4 The bistrifluoromethyl adamantane (24 cm 3; 33.67 g; 0.123 mol) from Example 1 was charged to a preheater in a quantity of 0.247 cm 3 / min. The preheater temperature was 250 ° C, and the CoF3 reactor temperature was graded from 250 ° C in zone 1 to 300 ° C in zone 4. The product line was maintained at 225 ° C. After all the hydrocarbon had been charged to the reactor, the reactor was purged with nitrogen for 3.25 hours. The crude product weighed 46.0 g.

This material was washed with water until the pH of the water. This material from the second stage was dried over molecular sieves overnight and then re-charged with 45.84 grams at a rate of 0.764 cm 3 / min. in the reactor, which was divided into temperatures from 275 ° C in zone 1 to 380 ° C in zone 4 for the final step. The reactor was purged with nitrogen for 4 hours before removing the product receiver, which contained 47.8 g of fluorocarbon; 75% material balance. Gel chromatography analysis 4 showed that the product contained 90% perfluoro-1,3-dimethyl adamanane (m.p. 6806), which was confirmed by mass spectrography and 19 pF NMR. A similar run was made with 1,3-bis (trifluoromethyl). .7-dimethyl adamantane, whereby a 55% yield of perfluorotetramethyl adamantane (m.p. 13800) was obtained.

EXAMPLE 5 V The following examples illustrate the results obtained when the first (partial) fluorination step according to the invention e is not used. Exo-tetrahydrodicyclopentadiene (25 cm; 25.15 g; 0.1776 mol) was charged to a preheater at a rate of 0.494 cm 3. The temperature of the preheater was the temperature of the 3-reactor so that it 7802153-2 ranged from 200 ° C in zone 1 to ZSOOC in zone 4. The product line was maintained at ZZSOC After all 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 washed with water until the pH of the water was 5.

The material from the second step was dried over molecular sieves overnight, and then 55.84 g was recharged at a rate of 0.764 cms / min. in the reactor, which was divided so that the temperature was SOOOC in zone 1 and 37500 in zone 4 for the last step. The reactor was purged with nitrogen for 4 hours before the product receiver was removed, which contained 60.8 g of fluorocarbon; 87% material balance calculated on invested 24.15 g of THDCP.

Gel chromatography analysis showed that the product contained 40% endo- and exo-perfluoro-tetrahydrodicyclopentadiene, 45% perfluorobicyclo [δ, 5.0] decane and 15 v 15% unknown fluorocarbons.

EXAMPLE 6 Exo-tetrahydrodicyclopentadiene (35 g) is slowly added to a slurry of MnF 3 (0.45 kg) 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 hours. The product is extracted with "Freon 113" and distilled to remove both "Freon 113" and perfluoro (1-methyl) decalin. The distillation residue consists of partially fluorinated tetrahydro-cyclopentadiene, in which the average molecule contains approximately 7 fluorine atoms: CIOHQF7.

When the partially fluorinated tetrahydro-dicyclopentadiene thus obtained is subsequently perfluorinated with CoF3 in accordance with the procedure of Example 4, substantially pure exo- and endo-perfluorotetrahydrodicyclopentadiene (bp 180-Z2SOC) is obtained in high yield, which product is substantially free of the by-products mentioned in Example S EXAMPLE 7 Following the procedure of Example 6 but using partially fluorinated camphane, hydrogenated pinan, 1,4-methanodecalin or 1,4,5,8-dimethanodecalin instead of partial fluorinated tetrahydrodicyclopentadiene, the corresponding perfluorinated cyclohydrocarbon is obtained in high yield and substantially free of any degradation by-products in the form of open ring products. EXAMPLE 8 7802153-2 Product from Boiling point fluorinated camphor 141 - 144 ° C hydrogenated pine 140 - 142 ° C 1,4-methanodecalin 159 - 160 ° C 1,4,5,8-dimethanodecalin 177 - 179 ° C As discussed above undergoes e.g. fluorolefins and acetylenes facilitate Diels-Alder-type reactions and act as di-enophiles in 1,4-cyclo-addition reactions; their reactivity to dienes is usually higher than for corresponding hydrocarbon analogs. The following examples illustrate the preparation of partially fluorinated cyclohydrocarbons, which can then be completely fluorinated according to the conditions of Example 4 to produce perfluorocyclohydrocarbons in high yield and substantially free of ring-opened by-products: 1,3-cyclohexadiene (1 mole is reacted with 25% molar excess of hexafluoropropylene for 24 hours at about 150 ° C to give 2- (trifluoromethyl) -2,3,3-trifluorobicyclo [2.2.2] octane (b.p. 120-IZSOC Hydrogenation over radium gives 2- (trifluoromethyl) -2,3,3-trifluoro-bicyclo [2.2, Z] octane.

EXAMPLE 9 Norbornadiene (1 mol) and a 24% molar excess of hexafluorocyclopentadiene are heated for 24 hours at 100 DEG C. to give, which after treatment with COF3 according to the procedure of Example 4 gives high purity perfluoro-1,4,5,8- dimethanodecalin (b.p. 159-161 ° C).

EXAMPLE 10 In the same manner as in Example 3, 1,3-dimethyl adamantane (22 g) is slowly added to a slurry of KCoF 4 (0.45 kg) in perfluoro-1-methyldecaline. When all the hydrocarbon has been added, the mixture is heated with rapid stirring to 200 ° C for 24 hours.

The product is then extracted with "Freon 113" and distilled to remove both "Freon 113" and perfluoro-1-methyldacelin. The distillation residue consists of partially fluorinated 1,3-

Claims (6)

7802153-2 dimethyl adamantane, wherein the average molecule contains approximately 10 fluorine atoms, e.g. CIZHIOFIO. Since proportionally more catalyst was used for the starting material than in Example 3, the fluorination is higher and in this case represents 50% yield of the hydrogen atoms. 1. Process for the perfluorination of non-aromatizable polycyclic hydrocarbons, characterized in that: (1) partially fluorinated a polycyclic hydrocarbon selected from alkyl adamantanes having 11 to 50 carbon atoms, endo- and exo-tetrahydrodicyclopedadiene, hydanethane , camphor, bicyclooctanes and bicyclononanes by contacting it in a first reaction zone with a fluorinating agent selected from the group consisting of MnF3, SF4, KCOF4 and fluorolefins, in liquid phase up to about 50% fluorination corresponding to perfluorination; 2. [2] thereafter, said partially fluorinated polycyclic hydrocarbon further fluorinates in vapor phase in a second reaction zone with CoF 3 at a temperature not higher than about 50 ° C above the boiling point of the fluorinated material, to form a highly fluorinated material with a degree of fluorination corresponding to a maximum of about 75-95% of perfluorination; and (3) recovering and recycling said highly fluorinated material to the second reaction zone and bringing it into new contact with CoF3 in vapor phase at temperatures which are about 100 ° C higher than those first used in (2) above, to provide a substantially perfluorinated polycyclic hydrocarbon. Process according to Claim 1, characterized in that the temperature in the first reaction zone is in the range from about 17 ° C to 50 ° C. 7so21sz-2 10 Process according to Claim 1 or 2, characterized in that the temperature in step (2) is divided so that it varies from immediately 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. A method according to any one of claims 1-3, characterized in that the temperature in step (3) is divided so that it varies from about 100 ° C above the boiling point of the recycled material in the first part of the the second reaction zone to about 150 ° C above the boiling point in the last part of the reaction. Process according to any one of the preceding claims, characterized in that the fluorinating agent in the first reaction zone is SF4 and that the polycyclic hydrocarbon is an alkyl adamantane in the form of a carbonylated derivative thereof. Process according to one of the preceding claims, characterized in that the alkyl adamantane is 1-ethyl adamantane, 1-methyl adamantane, 1-ethyl-3-methyl adamantane or 1-ethyl-3,5-dimethyl adamantane.