SE448371B - PROCEDURE FOR PERFLUORING THE NON-AROMATIZABLE POLYCYCLIC CULVET - Google Patents

Description

The latter starting material comprises non-aromatizable polycyclic hydrocarbons selected from the group consisting of alkyl adamantanes, as described in U.S. Pat. No. 3,641,167, and having 11-30 carbon atoms, preferably 12-14 carbon atoms. such as 1,6-dimethylladamantane, sd1; 3,5-trimethylladamantane; 1-ethyl adamantane, 1-methyl adamantane, 1-ethyl-3-methyl adamantane, 1-ethyl-3,3-dimethyl-pd adamantane or the like; endo- and exo-tetrahydrodicyclopentadiene; methanodecalines such as 1,4-methanodecalin or 1,4,5,8-dimethanodecalines; hydrated pain; kamfan; bicyclooctanes; bicyclone nonanes; 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 high purity V, with at least 95% of the hydrogen atoms and more preferably from 97-100% being replaced by fluorine atoms. In general, in this improved process, the conversion of the starting material to the corresponding perfluorinated compound is at least 50% and usually about 90% or more. These perfluorinated materials are useful in a variety of different industrial and pharmaceutical applications. The fluorinated alkyl adamantanes, for example, are useful as coolants for sauna turbine engines, dielectric coolants for transformers, generators and the like, as well as as components in synthetic blood compositions, perfusion media and similar biological applications. The perfused cyclic materials are also useful as working fluids in heating pipes and Dankin bicycle motors.

The partially fluorinated hydrocarbon from which the starting process of the invention is prepared can be prepared by contacting the polycyclic hydrocarbon or its hydroxylated or carboxylated derivatives thereof, depending on the fluorinating agent used, in liquid phase with a fluorinating agent selected from the group consisting_of HF; HF-pyridine complexes, AgF2, MnF3, SF4, SbF5, 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 controlled by appropriate choice of medium and starting material. In general, a transposition. of from about 3 to 6 fluorine atoms in the hydrocarbon has been found to stabilize the material for the more difficult conditions used in the .c- w 15 I 20l¶, 25., 30 35 'foam. 44so371t¿ 3 taruttömmandekflnorering med t¿ek. CoF¿. Usually, in this step of partial fluorination, the above-mentioned fluorinating agent 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 dialkylamino sulfur fluoride. Thus, in case of alkylamantanes, For example, these compounds are first converted to the corresponding ketones, aldehydes, acids or hydroxy derivatives before they can react satisfactorily with the SFA or dialkylamino sulfur reagent. Examples of methods for preparing these adamantyl carbonyl derivatives are available. U.S. Pat. Nos. 3,556,740 and 3,356,741 to adamantyl ketone and diketone derivatives; U.S. Pat. Nos. 3,250,805 (adamantyl dicarboxylic acids); U.S. Patents 3,383,424, 3,356,718 and 3,356,709 (adamantyl dihydrocarbides; Other similar reactions are likely to be apparent and will be appreciated by those skilled in the art. Such carbonylated polycyclic starting materials are prepared in accordance with similar prior art. From the above it thus appears that when the partial fluorination (i.e. in the precursor) of the polycyclic starting materials are generally mentioned, this fluorination in all cases is intended to include the carbonyl derivatives of the material when SF4 or dialkylamino sulfur fluorides are used as fluorinating agents. In addition to the use of carbonyl derivatives of cyclic materials to be perfluorinated when SF4 is used, mention may be made of the use of analogous known alcohol derivatives of these compounds, when HF or HB-pyridine complexes constitute the partial fluorinating agent, and chlorinated or brominated derivatives , when SbF5 was used. Furthermore, cyclic dienes, such as 1,3 + cyclohexadiene, can also be reacted with fluorolefins, such as hexafluoropropylene, in a Diels-Age type reaction, to produce 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. I r * “The above-mentioned DíelsfAlder reaction products are so? also intended to be included in the general definition of the partially fluorinated polycyclic hydrocarbons, which are then perfluorinated with 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 perfectly fluorinated, and thus stabilized, cyclic hydrocarbon, regardless of how it is produced.1 7 gt d The degree of fluorination which is necessary to impart structural stability to the molecular materials; before reacting with COF3 in the first and second 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-percent exchange of such hydrogen with fluorine; The location of these fluorine atoms can be either in the nucleus or in the side chain of the hydrocarbon molecule, or in both parts. Accordingly, it is to be understood that the fluorinated product may in the first instance be either a single product or a mixture of partially fluorinated materials depending on the fluorinating agent used.

This product should, before being brought into contact with CoF3 in the subsequent step, first be separated from the first fluorinating agent, preferably by distillation {dg. In the first step of the process, the aim is to provide as high a degree of fluorination as possible. possible without destroying or degrading the ring structure of the association. The effect of this fluorine ring 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 first stage, which usually falls outside the fluorination by no more than 5-25%, is easily accomplished by contacting the partially fluorinated hydrocarbon mixture with the vapor phase of COF3 (by heating). moderate batch ~ Z ning rate and at a temperature ranging from immediately above the boiling point of the batch 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 509 degrees above. Since the reaction is ecothermal, care should be taken to control 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 recirculating the highly fluorinated product from the COFS reaction back into the same reactor, which this time is heated to a considerably higher temperature, preferably about 10,000 higher, above the thermally graded reactor. to achieve substantially complete perfluorination and to achieve yields of about 50-95%, based on the amount of raw material originally charged. _. The perfluorinated product is then suitably cooled to a temperature of from ~ oa-0 ° C to 8006 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 in 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. In Adamantanaicarboxylic acid (zz, 4 g-0.1 moi) and sr4 (z7, g g - 25% excess), the ice pressure bomb was heated for 24 hours at 110 ° 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 bistri-fluoromethyl adamantane ($ 0% yield); kpr 7106 vid_10 mm Hg.

. EXAMPLE 2 § iei '' s; 1> dimery1-1, s-adamantanaicaboxyic acid (zs; z g-0.1 ml) and SF¿g (27¿Q g-25% excess) were heated and worked up as in Example 1 to give 18 g of 1,5-dimethyl-5,7-bis (trifluoromethyl adamantane (60%); bp; 80-8300 at 0.5 mm Hg; mp 58 ° C, EXAMPLE 3) 3-Dimethyl adamantane (42 g) was slowly added to a slurry of MnF 3 (0.45 kg) in perfluoro-1-methyldecaline. 20,000 for 24 hours, and the product was extracted with "Freon 113" and distilled to remove both VFreon '1 T13 "and perfluoro-1-methyldecaline. The distillation residue was made up of partially fluorinated 1,3-dimethyl adamantane, in which through. ..., .._, ...__..._.... ..._.........___._._ P -.-._ V> - 10 '15, The fluorine differs from the ZZOOC in zone 1 to the ZSOOC in zone 4. The product line>, 44sl371p, 2 * 2 ii * 6 the average molecule contains approximately 8 fluorine atoms, e.g.

EXAMPLE 14 2 f p se p I Bistrifluoromethyl adamantane (24 cm 3; 33.67 g in 9.123 mol) from Example 1 was charged to the preheater in the quantity of 0.247 cms / min. The temperature of the preheater was_50 ° C, and the CoF3} reaction temperature was graded from 250 ° C to * 1 in zone 1 to 30 ° C in zone 4. The product line was maintained at 2 ° 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 was 5; This material from the second step was dried over mol-7 sieves overnight and then re-charged with 45.84 grams at a rate of 0.764 cms / min. in the reactor, which was divided into 7 temperatures from z7s ° c'i zone 1 to sso ° c 1 zone 4 for the last stage. The reactor was purged with nitrogen for 4 hours before: removing the product receiver, which contained 47.8 g of fluorocarbon; 175% material balance. Gel chromatography analysis showed that the product contained 90% Vperflnor-1,3-dimethyl adamantane (m.p. 6800), which was confirmed by mass spectrography and 19 μM NMR.e 2 eA similar run was made with 1,3-Abis (trifluoromethyl) ¥ 45,7-dimethyl adamantane a 55% yield of per-2 1ss ° c) was obtained. The following examples illustrate the results obtained when the first (partial) fluorination step was not used.

Exo-tetrahydrodieyclopentadiene (25 cm 3; 25.15 g; 0.1l76_ mol) was charged to a + heater at a rate of 0.494 cm 3 / min. The temperature of the preheater was that the temperature of the 3-reactor was set to maintain it at 22,500. After all the hydrocarbon had been charged to the reactor, the reactor was purged with nitrogen for 3.25 hours. Raw pro- m; The product weighed 63.6 g. This material was washed with water until the pH value of the water was 5. d In the material from the second stage, it was dried over mole sieves overnight, and then 55.84 g was recharged at a rapidity. of the 0.764 cms / min} ¿i reactor, which was divided so that the temperature was 300 ° C in zone I and 375 ° C in zone 4 for the last t "f le1o '' 15 20 ZS l 30 ssa e ring. 448 571m], 'n' _-_ I m increased; The reactor was purged with nitrogen for 4 hours before removing the product receiver, which contained 8 g; 8 g of fluorocarbon; 87% material tail_counted on_charged 24.15 g of THDCP.

Gel chromatographic analysis showed that the product contained 40% endo-7 and exo-perfluorophenetrahydrydicyclopentadiene, 45% perfluorobi-L * cyclo [§, 5, Q} decane and 15% unknown fluorocarbons, - 'Exo; tetrahydrodiCyclopemtadiene (35 g) to a slurry of MHFÉ (Q, 45 kg) in perfluoro (1-methyl) decalin - - EXAMPLE - en - - - 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 Frebn 113 "as perflorous (1-methyl) decalin." with the procedure of Example-4, substantially pure 'exoe' and endo-perfluorotetrahydrodicyclopentadiene (b.p. 180-225 ° C) are obtained in high yield, which product is substantially free of the by-products mentioned in Example 5.

Ex3MP5L'7 "a 9 'hpl according to the procedure of Example 6 but using perfluorinated fluorinated hemp, hydrogenated planene, 1,4-methano-I decalin or 1,4, S, 8E-dimethanodecalin instead of partial flu fluorinated water fi etrahopentrity, the corresponding proportion of hydrofluorocycled cyclohydrocarbon is obtained in high yield and substantially free of any leaching by-products in the form of products with open product from I 7 7 Boiling point of the flame-retardant l-1414 - 14s ° c hydrated pinan 140 - 142 ° c :; nødeka1inl = v 159 - 161 ° c ÃÖ1,4, s, s = @ 1metanodeka11n '177 - 179 ° c EXEMPBLfs *' l_ v vv vrr I h Sâ§0m omtalats Ovan uñdergåritrex. Fluorolefins and two-membered reactive compounds of the DielsÉAIdèr-type Qch. act as dl-enophiles in T, 4-cycloAddition reactions; their reactivity to give the pepper fluorocycolyates in high yield and easy conversion of the hexafluotopropylene for 24 hours at about 150 DEG C. to give 2-trifluoromethyl) -2,3,3-trifluoro-bicyclo [oct], 2,3 EXAMPLE 9 448 3711 eí _. _, 78 geñtemet dieher är vànllgem högte än för equivalentne hydrocarbon-e analogues; The following examples show the preparation of partially fluorinated cyclocohydrogens, which can then be completely fluorinated in accordance with the conditions of Example 4 in substantially free ring-opened by-products; (1) 3 cyclohexadiene is reacted with 25% (25%). bp 120-123 ° C). Hfdrering¶öÜer radium ger 2- (trifluoromethyl) - ~ z, s, zfcrifluør-bicyklofg, z, ¿1oktan. The norbornadiene (1 mole) and a 24% process molar excess of hexafluorocyclopentadiene fi are heated for 24 hours at 100 ° C to form which, after treatment with CQF3 according to the procedure of Example 4, gives high perfluoro-T, 4, k, kf. 159 + 161 ° C) .te EXAMPLE 10 _ e _. «T-In the same way_spm in Example 3, the 1,3-dimethyl adamantane (22 g) was slowly added to a suspension of KCoF4_ (0; 4S.kg) in perfluoro- 1-methyldecalin. When all the hydrocarbon has been added, the mixture is heated to a rapid conversion to 100 DEG C. for 24 hours. The product is then extracted with "Ffeon 113" oçhzdestíllerás to remove both "Freonl113VÜsom": perfluoro-1-methyldecalin.

The distillation residue consists of partially fluorinated 1,3-dimethyl adamantane, wherein the average molecule contains approximately e10 fluorine atoms, e.g. C12H10F10. Since proportionally more catalyst is used for the starting material than in Example 3, the fluorination is higher and in this case represents 50% yield of the hydrogen atoms. th)

Claims (1)

1. -sr de1en.av'reactionzonen. 448 mi "dPATRENITE CURRICULUM / '4l.i ¿Procedure for the perfusion of non-aromatizable polycyclic hydrocarbons; the clen ent only by the fact that one: ~ ..: al) 1 fluorinates a partially fluorinated polycyclic hydrocarbon down-hydrocarbon In a reaction zone at a temperature not exceeding about 50 DEG C. above the boiling point of the fluorinated material, to form a highly fluorinated material having a degree of fluorination corresponding to a maximum of about 95% -7% perfluorination; "a2) recovering and recycling said highly fluorinated material to said reaction zone and bringing it into a new contact with Cofs in the vapor phase at temperatures which are about 10006 higher than those first used, to form 1 a substantially perfluorinated polycyclic hydrocarbon. Process according to claim 1, characterized in that the temperature in step 1 is divided so that it varies from just above the boiling point of the charged material in the first part of the reaction zone to about SUOC above the boiling point in the last. A method according to claim 1 or 2 ,. characterized in that the temperatures in step (2) are divided so as to vary from about 100 ° C above the boiling point of the recycled material in the first part of the reaction zone to about 150 ° C above said boiling point in the last part of the reaction zone. : e4; A process according to any one of the preceding claims, characterized in that the partially fluorinated hydrocarbon is a partially fluorinated adamantane. 5. A process according to any one of claims 1 to 3, characterized in that the partially fluorinated hydrocarbon is a partially fluorinated tetrahydrodicyclopentadiene. vi d6. A process according to any one of claims 1 to 3, characterized in that the partially fluorinated hydrocarbon is a partially fluorinated bicyclooctane or bicycloheptane. 7. A process according to any one of claims 1-3, characterized in that the partially fluorinated hydrocarbon is a partially fluorinated methanodecalin. _. ,, _