PREPARATION OF DERIVATIVES

Abstract: The present invention relates to the chemical modification of generally inert compounds containing at least one perfluorocarbon moiety of the general formula R<1>R<2>R<3>C-F wherein each of R<1>, R<2> and R<3> may represent F or a substituted carbon moiety or two or three of R<1>, R<2> and R<3> together represent a substituted carbon moiety bound to the fluorinated carbon by a multiple bond. The method comprises the steps of reacting this generally inert compound with a compound which in its ionised form has the general formula Z<-> M<+> wherein Z<-> represents nucleophile and M<+> represents a gegen-ion, in a medium favouring the ionised form so as to form a corresponding compound wherein at least one said fluorine has been displaced by said nucleophile. By means of the process of the present invention it is possible to prepare derivatives of perfluorocarbon compounds under relatively mild reaction conditions thereby avoiding degradation and/or unwanted side reactions.

Description: - 1 PREPARATION OF DERIVATIVES The present invention relates to the chemical modification of perfluorocarbon compounds, including compounds containing at least one perfluorocarbon moiety. S Perfluorocarbon compounds are of considerable economic importance not least because of their substantial inertness and resistence to chemical attack. This does however severely limit the possibility of preparing derivatives of such compounds and of modifying 1° the properties of such compounds. It is an object of the present invention to avoid or minimise one or more of the above disadvantages. The present invention provides a method of chemically modifying a perfluorocarbon moiety of a generally 15 inert compound containing at least one perfluorocarbon moiety of the general formula R 1 R 2 R 3 C-F wherein each of R1, R2, and R 3 may represent F or a substituted carbon moiety or two or three of R 1 , R- ~ and R- ' together represent a substituted carbon moiety bound to the ZQ fluorinated carbon by a multiple bond, which method comprises the steps o reacting said generally inert compound with a compound which in its ionised form has the general formula Z~M + wherein Z" represents a nucleophile and M + represents a gegen-ion, in a medium Z5 favouring said ionised form, said generally inert compound being provided with an electron donor, so as to form a generally corresponding compound wherein at least one said fluorine has been displaced by said nucleophile. 1Q-. Conveniently there, is used a strong nucleophile which also constitutes a said electron donor in said medium, though alternatively there may be used a separate electron donor as further described herein- below. Thus in a preferred aspect the present invention provides a method of chemically modifying a per- fluorocarbon moiety of a generally inert compound containing at least one perfluorocarbon moiety of the general formula R3-R 2 R 3 C-F wherein each of R 1 R 2 R 3 may represent F or a substituted carbon moiety or two or three of ^, R 2 and R 3 together represent a substituted carbon moiety bound to the fluorinated carbon by a multiple bond, which method comprises the steps of reacting said generally inert compound with a compound which in its ionised form has the general formula Z~ M + wherein Z~ represents a strong nucleophile and + represents a gegen-ion, in a medium favouring said ionised form so as to form a generally corresponding compound wherexn at least one saxd fluorxne has been displaced by said nucleophile. It will be appreciated that by control of the nature of the reagents and the substrate, the reaction conditions and/or duration, the degree of fluorine displacement can be limited -if desired, for example in order to maintain a degree of inertness in the compound though normally the reaction is allowed to proceed to completion. For the avoidance of doubt it should also be understood that the above definitions of ^, 2 , and R 3 include within the scope of the present invention generally inert compounds containing one or more non- substituent hetero atoms as for example in the rings of heterocyclic compounds, such hetero atoms including N, S, 0, Se, Te and P atoms, e.g. as in N-fluoroperfluoro-morpholine and - piperidine. Moreover the above definitions also include generally inert compounds wherein two or three of R1, R2, an( 5 R3 represent a moiety which, together with the carbon atom to which they are bound constitutes a ring structure. The process of the present invention may be carried out undqr any suitable temperature and pressure 5 conditions, including ambient conditions in at least some cases. In general though it will be appreciated that elevated temperatures e.g. up to the reflux temperature of the reaction medium will result in shorter reaction times. In many cases though Iø reasonable reaction times of only a few hours or even only minutes may be obtained at temperatures significantly below the reflux temperature. Whilst in general the reaction proceeds satisfactorily at ambient pressure superatmospheric pressures may also be used, e.g. up to 120 kbars, especially in those cases where there is a negative volume of activation. Low pressures e.g. down to 10~ 3 torr may also be used. Efesirably the method is carried out in a non-oxidising, oxygen-free, atmosphere in order to avoid unwanted zσ side-reactions. If desired an inert gas e.g. argon atmosphere may be used. Naturally with the generally relatively mild reaction conditions which.can be used in the process of the invention, the risk of unwanted side reactions and degradation of reaction products Z5 tends to be reduced. This may be contrasted with the relatively severe conditions required in previous 4 _ attempts at modification of such compounds, see for example "Preparation, Properties and Industrial Applications of Organo-fluorine compounds". Edited by R.E. Banks, Pub. Ellis-Hσrwood Ltd. (1982), p.221, and "Fluorine in Organic Chemistry" by R.D. Chambers, Pub. John Wiley, U.S.A. (1973, p. 141). It will be appreciated that by controller the reaction conditions and/or duration, the degree of fluorine dis¬ placement can be limited if desired, for example in order to maintain a degree of inertness in the compound though normally the reaction is allowed to proceed to completion. Various suitable media are known in the art favour¬ ing the existence of strong, ionised, nucleophiles. Thus on the one hand there may be mentioned dipolar aprotic solvents which produce a high degree of sol- vation such as„l, 3-dimethylimidazolidinone (DMEU) , hexamethylphosphortriamide (HMPA) , or N methylpyrrol±reor N, -dxmethylformamide (DMF) . On the other hand there m ay be used other relatively inert solvents having adequate solvation capability such as aromatic hydro¬ carbons e.g. benzene, toluene etc., ethers such as diethylether, tetrahydrofuran, etc., liquid nitriles e.g. acetonitrile and benzonitrile, and polyethers e.g. monoglyme which isCH3p(CH2)2 OCH3 and longer chain analogues i.e. polyglymes, together with a suitable sequestering agent. Various sequestering agents are known in the art including cryptands e.g. cryptand (2.2.1) which is 4, 7, 13, 16, 21 -pentaoxa-1, 10-diazabicyclo-(8,8,5)- tricosane which is especially suitable for use with a sodium gegen-ion and cryptand (2.2.2.) whic is especially suitable for use with a potassium gegen-ion; crowns e.g. 18- crown-6 (1,4,7,10,13, 16-hexaoxacyclo octadecane) which is particularly suitable for potassium gegen-ions and 15- crown-5 which is particularly suitable for sodium gegen-ions; and other complexing agents such as polythioether or other analogues of the above compounds. Further details of sequestering agents may be found in the literature and standard text books such as "Inclusion Compounds" edited by J.L. Atwood, J.E.D. Davies and D.D. MacNicol, Academic Press, London, 1984, Vols. 1-3 Most preferably there is used a dipolar aprotic solvent together with a sequestering agent. Particularly suitable nucleophiles are the anions of compounds of the general formula Q X M V in which Q represents an atom of oxygen, sulphur, selenium, tellurium, carbon, silicon, phosphorus, nitrogen, arsenic, antimony or bismuth, normally substituted by one or more of optionally substituted alkyl, aryl, aralkyl and other functionalised groups, e.g. (CH2)2~ ~~~~ 2 ; M is a gegen-ion forming atom such as an alkali or alkaline earth metal e.g. sodium, potassium, lithium, rubidium or cesium, (preferably sodium or potassium) , magnesium, calcuim, strontium or barium, or a suitable organic action resistant to nucleophilic attack; and x and y are integers such that x times the valency of Q is equal to y times the valency of M. Thus it will be appreciated that the nucleophiles Z used in accordance with the present invention include a wide range of agents with various degrees of negative electrical charge. Suitable nucleophiles that may be mentioned include benzene thiolate and other arene thiolates; thiolates such as those corresponding to l-amino-2-mercaptoe- thane and longer chain analogues thereof wherein the amino group may be replaced by another nuσleophillic centre also capable of reacting with an epoxide or other suitable moiety; and thiolates corresponding - 6 - to 6-mercapto-6-deoxy and other like analogues of o - β - and # * - cyclodextrins and derivatives thereof, crowns, cryptands, and or other complexing agents capable of binding ionic or molecular guest 5 species which may or may not carry an electrical charge. It will also be appreciated that the new derivatives provided by the process of the present invention may in turn be further treated thereby opening up the way to an even greater number of possible derivatives• ® Thus for example there could be used a thioacetate nucleophile to provide a thioacetate derivative of a generally inert perfluorocarbon compound which could then be hydrolysed under generally conventional con¬ ditions to the corresponding merca tan which may then 5 be reacted under alkaline conditions with 6-monotosyl » - ζC - cyclodextrin to provide a corresponding to Oi - cyclodextrin derivative. The latter product is particularly valuable for use in chromatographic columns for the optical resolution of mixtures of 0 different optically active isomers. Various substantially inert and often heretofore underivatisable perfluorocarbon compounds may be modified in the process of the present invention including cyclic, especially polycyclic saturated 5 andunsaturated perfluorocarbon compounds such as perfluorodecalin, and perfluorocyclohexene, polymeric perfluorocarbon compounds such as polytetrafluoroethylene and cσpolymers of perfluoropropene with tetrafluoroethylene, and 0 saturated and unsaturated alkyl and aralkyl per¬ fluorocarbon compounds such as perfluoroisobutane, perfluromethylcyclohexane, and perfluoro - 1,2-diphenylethane, perfluoro-1-dodecene and CF3 (C 2) n ~CF=CF2, an <i including such compounds containing substituents which do not substantially interfere with the displacement of the fluorine, e.g. ether groups wherein the alkoxy moiety_ is also susceptible to being replaced by the nucleophile ^ in the course of the reaction. In the case of saturated compounds these may conveniently be subjected to a preliminary electron beam bombardment using techniques such as those described in East German Patent Publication No. I DD151,156 to produce corresponding unsaturated compounds which then react particularly rapidly in the method of the present invention. It is also possible in accordance with the present invention to use less strong nucleophiles and/or 15 to obtain an increase in reactivity providing improved product yield and/or rate of formation or to facilitate reaction with systems otherwise more or less unreactive by providing an electron donor to the generally inert perfluoro compound in the 20 reaction medium. Thus there may be added to the reaction medium sodium or other suitable electro¬ positive metal; or single-electron donors such as the napthalenide radical anion and Co(I) " "supernucleophiles" such as cobalamin, cobaloximes and 25 other Co(I) chelates. Alternatively the reaction medium may be bombarded with electrons from cathodes, β-emitters or other system discharging electrons. It will be appreciated in this connection that by using suitable screening masks with electron 0 "bombardment" it may be possible selectively to "print" chemically modified areas onto a larger body of the perfluorocarbon compound. Advantageously also there may be used in the reaction medium a fluorinated or other generally 5 inert cosolvent, which should desirably - 8 be more inert than the perfluorocarbon compound of the general formula R 1 R 2 R 3 C-F being treated, so as to increase transfer of said compound into the reaction phase of the nucleophile or of the nucleophile into the perfluorocarbon moiety phase. Thus for example where a less inert perfluorocarbon compound such as perfluorodecalin is being treated there could be empl¬ oyed a more inert consolvent such as perfluoro-n-heptane. Furthermore there could also be used specific phase 1C transfer agents such as for example perfluoro-18-crown- 6 in a generally similar manner. Again it will be appreciated that the phase transfer agent should be more inert than the compound being modified in order to avoid preferential modification of the perfluoro- 15 carbon moiety thereof. It will also be appreciated that the particular above-mentioned transfer agent would also have a se'questering capability. Amongst other compounds that may be modified by the method of the present invention are the perfluoro- -^ perhydrocarbon derivatives of linear acenes including napthalene, anthracene, tetracene, pentacene, hexacene and heptacene, branched acenes such as phenanthrene, and the cyclic analogue; coronene, as well as pyrene and triphenylene and other condensed aromatic and 55 heteroaromatic and linked e.g. biphenyl aromatic systems so as to form the corresponding fully substituted aromatic compounds. Thus for the first time the present invention opens up the possibility of producing fully substituted derivatives of such compounds by applying £T the method of the present invention to the perfluoroper- hydrocarbon derivatives of such compounds, which derivatives can conveniently be obtained by means of reaction with a reagent such as C0F3 as further described by D. Harrison et al in • • Tetrahedron (1963) JL9. P.1893. Thus for example tetracene may be treated with C0F3 to produce perfluoroperhydrotetraσene which can then be reacted with a suitable nucleophile so as to produce 5 dodeca-substituted tetracene. Such compounds are particularly valuable as clathrating agents. In a further aspect the present invention provides as novel compounds fully substituted linear acenes, coronene, pyrene and triphenylene. 0 As noted hereinabove, perfluoro-based organic polymers now represent a highly significant world-wide market, but the desirable properties of these parent polymers cannot be incorporated into novel systems owing to their substantial inertness. The process of 15 " the present invention now allows though the modification of such polymers as PTFE (Teflon), FEP (Teflon 100), Viton A, polyvinylidene fluoride so as to provide efficient binding sites thus opening up the possibility of achieving ' good adhesion to metal, wood, 2D: glass, plastic and other substrates in a relatively simple and economic manner. Thus for example by using a nucleophile such as ~S(CH2)2 NH 2 there may be obtained a derivative which will react with epoxy or other suitable groups in another compound to achieve powerful ZΞr chemical bonding such as that obtained in epoxyresin adhesives. The introduction of such modification, especially at the surface of a film or other body of such a compound, has many desirable applications whilst - 10 retaining the advantageous physical properties and chemical inertness of the patent fluoropolymer. Treatment of one face of the inert perfluoropolymer to be bound to a metal (for example) surface will provide protection from corrosion, will inhibit marine fouling and will reduce frictional resistance in water. Surface modification of perfluoro polymer-.-based chromatography column packing, for example, incor¬ porating chiral components can now be effected. Also packings capable of withstanding relatively seve_feelution conditions may now be obtained. Modified materials for novel membranes, printed-circuits, and printing surfaces may also be obtained as well as new polymer-bound reagents. Further preferred features and advantages of the present invention will appear from the following detailed examples given by way of illustration of the present invention. 5 EXAMPLE 1 Preparation of octakis(phenylthio)naphthalene (C - (SC ^HQ^). A - Preparation of Nucleophilic Reagent In a flushed 100ml three-necked flask equipped 10 with a reflux condenser, a three-way tap with a balloon connected to an argon cylinder, a rubber septum and a stirrer, was placed 0.7422g (18.56mmol) of sodium hydride 60% dispersion. Sodium dried pentane was used to wash the protective oil (normally present in 15 commercially available sodium hydride) out in three aliquots of 50ml each. The hydride was then pumped free of pentane and the atmosphere of argon re-introduced. 15ml of freshly distilled THF was then added and the flask cooled to -78°C. With stirring 20 2.146g (19.51 m ol) of 97% benzenethiol dissolved in 45ml tetrahydrofuran (THF) was added and the reaction allowed to rise slowly to room temperature, allowing excess pressure to escape. Completion of the reaction was effected by reflux on a water bath. ^ : The flask was quickly transferred to a rotary-evaporator where the solvent was removed, and thereafter to a rotary oil pump until no further weight loss occurred. A ^H nmr of the salt d^-DMSO was used to establish the content of THF remaining; this was Ώ - measured at 1 mole salt to ca 2 /3 mole THF, giving an effective molecular weight of the complex of ca 180 a.m.u. B - Reaction of Substrate with Nucleophilic Reagent Into a 10ml round-bottom flask was placed 517mg ^ ; (2.87 mmol) of the sodium benzenethiolate complex and a stirrer bar. The flask was evacuated by way of a needle through a septum cap and into this was injected 22mg (0.048 mmol) of perfluorodecalin (mixture of cis/trans isomers) and 4ml of dry, degassed N,N-dimethylformamide (DMF) The reaction mixture was 5 stirred in an oil bath at 60-70°C for ten days. After this time the cooled mixture was poured into toluene (20ml) and washed with water (10 x 60ml) before drying over anhydrous sodium sulphate. The solvent was removed by rotary evaporation and the material ° dissolved in a small amount of chloroform. This solution was applied onto a preparative silica thin layer chromatography plate (20cm x 20cm, 0.25mm thick) and diphenyl disulphide removed by three elutions of 40 - 60°C petroleum ether fraction. A further elution in 5 chloroform/hexane (3/1) gave the separated product as an orange band Rf 0.42. This was extracted into chloroform and the s'olvent removed leaving 26mg (0.0262 mmol) of - octakis( henylthio) naphthalene a 55% yield. This material had properties fully in accord 0 with the title compound prepared by a different synthetic route and structure established by x-ray single crystal diffraction analysis^. Mass spectrum: m/e 992 (M + ) ; 883 (M + -CSC 6 Hs]} 774 (M+-2CSC 6 H 5 ]). 5 100MHz X H n.m.r. : (CDC1 3 )6.4 -7.3 (complex (m)) 25MHz 13 C n.m.r. : ό " ς (CDCl 3 ) 125.7(d), 126.5(d), 127.3(d), 128.5(d), 128.7(d), 129.6(d), 137.4(B), 138.7(s), 0 139. l(s), 140.9(e), 142.9(s). 3055cm- 1 (S) 735cπr 1 (S) 1581cm- 1 (S) 700cπT 1 (S) 1477cm" 1 (S) 686cm- 1 (S) 1440cm" 1 (S) Melting point : 205-206°C. The material also co-spots with the authenticated sample during TLC on silica plates in chloroform/hexane mixtures and on a C ] _g alkylated reverse phase plate (Rf 0.18,MeOH). No fluorine could be detected with 100 MHz 19 F n.m.r. EXAMPLE 2 Preparation of octakis(m-tolylthio)naphthalene Into a 25ml flask equipped with a rubber septum and a stirrer bar was placed 2.840g (19.45 mmol) of sodium m-tolylthiolate before evacuation through an inserted needle. After injecting 15ml of l,3-dimethyl-2-imidazolidinone (DMEU) the mixture was degassed by stirring under rotary-oil pump vacuum and then 200mg (0.433 mmol) of perfluorodecalin added. The reaction mixture was stirred at room temperature for eight weeks during which a red colour progressively developed in the initially colourless medium. The contents were then poured into 50ml toluene and washed with 10 x 300ml water. The organic phase was dried over anhydrous sodium sulphate and then the solvent removed on a rotary evaporator. The residue was dissolved in a small amount of chloroform and applied onto a preparative silica thin layer chro atography plate (20cm x 20cm, 0.25mm depth). Multiple elutions in 40-60°C petroleum ether fraction were performed until the disulphide was removed (monitoring by U.V.), and then a short elution in -I4- chloroform/petroleum ether (3/2) gave a red band Rf 0.44, which was extracted into chloroform. This yielded 93mg (0.0842 mmol) of octakis( -tolylthio) naphthalene, 20% yield. Crystals obtained on recrystallisation from toluene had properties fully in accord with the title compound prepared by a different synthetic route and established by X-ray single crystal diffraction analysis. iα Mass spectrum: m/e_ 1104(M + ); 981(M + -[SC 7 H73) ; 858 (M + -2[SC 7 H 7 3) 100 MHz ~ -E n.m.r. : £(CDC1 3 ) 2.15(12H,s)2.2 (12H,s) 6.2 - 7.1(32H,complex(s) ) 25MHz 13 C . n.m.r. :S C (CDC1 3 ) 21.3( q) ,124.4(d) ,125.4(d), 15 126.5(d) ,126.9(d) ,128.2(d), 128.4(d),129.3(d),137.3(s) 138.1(s),138.3(s),138.8(s) 140.0(s),144. 2(s). 0 I.R. : Λ.max (KBr disc) 3030cm" 1 (M] 2920cm" ■ !( ) 1590cm" 1 (s; 1575cm" (S) 1475cm" 1 (Si 1220cm" (M) 1170cm" 1 (M) 1120cm" (M) 1080cm" 1 (M] 1040cm" (M) S 1000cm" 1 (M] 875cm" (M) 855cm" 1 (M 780cm" rl (S) 690cm- 1 (Si 430cm"^(M) Melting point 156 - 157°C The material also co-spots with the authenticated O sample during TLC on silica plates in chloroform/hexane mixtrues and on a Cj_g alkylated reverse phase plate (Rf = 0.09, MeOH) . No fluorine could be detected by lOOMHz 19 F n.m.r. EXAMPLE 3 Preparation of hexakis(phenylthio)benzene) In a 10ml flask was placed 630mg (3.50 mmol) of the sodium benzenethiolate complex (as described in Example 1) and 4ml of DMEU. This was degassed by stirring under vacuum through a rubber septum and 7.5mg (0.029 mmol) of perfluorocyclohexene injected. After stirring for 72 hours the yellow mixture was taken up in 20ml toluene and washed with 10 x 60ml of water. The organic phase was dried over anhydrous sodium sulphate and the solvent removed on a rotary evaporator. The product was dissolved in chloroform and applied to a preparative silica TLC plate (20cm x 20cm, 0.25mm depth). The plate was eluted 6 times in 40-60°C petroleum ether fraction and once in chloroform to half-way. The yellow band was extracted and the chromatography repea ' ted for final removal of diphenyl disulphide and other U.V. active bands. After removal of solvent, 20mg (0.028 mmol) of hexakis(phenylthio)benzene was isolated, a 96% yield. The yellow crystals had properties identical with those of an authentic sample prepared by a different synthesis and structure established by X-ray singlecrystal diffraction. (A.D.U. Hardy, D.D. MacNicol, D.R. Wilson, J. Chem. Soc. Perkin II, 1979, 1011). Mass spectrum : m/e_ 726 (M + ) Melting Point 185 - 186°C 100 MHz '■ Ε. n.m.r. <δ (CDCl 3 ) 6.8-7.3 (complex( )) 25 MHz 13 C n.m.r. <S C (CDC1 3 ) 126.2(d), 128.2(d), 128.9(d), 137.7(e), 148.1(s). The prepared and genuine samples co-spotted on TLC using both normal and reversed phase systems. " 16 " EXAMPLES 4 and 5 Preparation of perfluoro ept-1-ene derivaties Other perfluoroalknes give unprecedented . reactivity by the above method as has been established by mass spectrometry for perfluoro hept-l « ene with sodium benzenethiolate JCTΠM 904^7 " and with p_- toluene thiolate " m/ e 1002 . The products correspond to ATS 7 7 C 7 F3 i n both cases. Example 6 Enhanced preparation of octakis(m-tolylthio) 0 naphtalene using sodium metal at elevated temperature Two reaction mixtures A and B were prepared from the same sources of perfluorodecalin, DMEU and sodium m tolylthiolate using the procedure of example 2, these being identical apart from the additional inclusion 5 of ca. 0.5g sodium metal in small pieces to B. A and B were reacted simultaneously in the same bath at 50°-60°C for five days before being worked up as des¬ cribed in example two with in the case of B additional removal and toluene washing of unreacted sodium from 0 the toluene solution bf product prior to water washing the combined toluene solutions. In this manner A (containing 0.125g perfluorodecalin, 10ml DMEU and 1.58g. gave 42mg (14% yield) of product whilst B (containing 0.120g. perfluorodecalin, 10ml. DMEU, 55 and 1.52g. of sodium m tolylthiolate) gave 133 mg (46% yield) product, both products have m.p. 156-157°C and co-spotting under TLC with authenticated samples of octakis (m-tolylthio) naphthalene. EXAMPLE 7 XT- Enhanced preparation of octakis (■ S-tolylthio) naphthalene using sodiummetal at ambient temperature Two reaction mixtures A and B were prepared from the same sources of perfluorodecalin, DMEU and - 17 sodium m-tolylthiolate using the procedure of example 2 these being identical apart ..from the additional inclusion of ca. 0.5g. sodium metal in small pieces to B. A and B were reacted simultaneously for eight weeks at ambient temperature before being worked up as described in example 2 with, in the case of B, additional removal and toluene washing of unreacted sodium from toluene solution of product prior to water- washing the combined toluene solutions. In this Q > manner A (containing 0.103g perfluorodecalin, 8ml DMEU and 1.30g. sodium m-tolylthiolate) gave 68mg of product (corresponding to 28% yield) whilst B (containing 0, I08g perfluorodecalin, 8ml DMEU and 1.37g. sodium m- tolylthiolate) gave lOlmg of product (corresponding to 40% yield) both products having .p. 156-157°C and co-spotting under TLC with authenticated samples of octakis (m-tolylthio) naphthalene.

Claims: - 18 - CLAIMS 1. A method of chemically modifying a perfluorocarbon moiety of a generally inert compound containing at least one perfluorocarbon moiety of the general formula R 1 R 2 R 3 C-F wherein each of R!,R 2 , and R 3 may represent F or a substituted carbon moiety or two or three of R1, R 2 and R 3 togehter represent a substituted carbon moiety bound to the fluorinated carbon by a multiple bond, which method comprises the steps of reacting said generally inert compound with a compound which in its ionised form has the general formula Z" M + wherein Z" represents a nucleophile and M + represents a gegen-ion, in a medium favouring said ionised form, said generally inert compound being provided with an electron donor, so as to form a generally corresponding compound wherein at least one said fluorine has been displaced by said nucleophile. 2. A process according to claim 1 wherein is used a medium comprising a dipolar aprotic solvent which produces a high degree of solvation. 3. A process according to claim 1 wherein said dipolar aprotic solvent comprises at least one of 1, 3- dimethylimidazolidinone (DMEU) , hexamethylphosphortriamide (HPMA) , N methylpyrrolidone", and N-dimethylformamide (DFM) 4. A process according to claim 1 wherein said medium comprises a generally inert solvent having some solvation capability in combination with a sequestering agent. 5. A process according to claim 4 wherein said solvent is selected from an aromatic hydrocarbon, a liquid nitriles and an ether. 6. A process according to any one of claims 1 to 5 wherein is included in the medium a sequestering agent selected from a cryptand and a crown. 7. A process according to claim 6 wherein is used a sequestering agent selected from cryptand (2.2.1), cryptand (2.2.2), 18 - crown - 6, and 15 crown - 5. 8. A process according to any one of claims 1 to 7 wherein said generally inert compound is saturated, said process includes the preliminary step of electron beam bombardment of said saturated generally inert compound so as to convert it to the corresponding unsat¬ urated compound. 9. A process according to any one of claims 1 to 8 wherein is provided an additional or complementary electron source in the reaction medium. 10. A process according to claim 9 wherein is provided an electron source selected from an electropositive metal or metal couple and other single electron donors. 11. A process according to claim 9 wherein the reaction medium is bombarded with electrons from the cathode, jB-emitter, or other electron discharge system. 12. A process according to any one of claims 1 to 11 wherein is used a strong nucleophile which constitutes an electron donor in said medium. 13. A process according to any one of claims 1 to 12 wherein is used a nucleophile comprising an anion of a compound of the general formula Q x M y in which Q represents an atom of oxygen, sulphur, selenium, tellurium, carbon, silicon, phosphorus, nitrogen, arsenic, antimony or bismuth, optionally substituted by one or more of optionally substituted alkyl, aryl, aralkyl and other functionalised groups e.g. ( H2 ) 2NH2 ; M is a gegen-ion forming atom such an alkali or alkaline earth metal e.g. sodium, potassium, lithium, rubidium or cesium, (preferably sodium or potassium) , magnesium, calcium, strontium or - 20 - barium, or other suitable electropositive metal, or a suitable organic action resistant to nucleophilic attack; and x and y are integers such that x times the valency of Q is equal to y times the valency of M. 14. A process according to claim 13 wherein is used a nucleophile selected from optionally substituted aromatic and aliphatic thiolates. 15. A process according to claim 14 wherein is used an arene thiolate. 16- A process according to any one of the preceding claims wherein said generally inert compound is reacted in the form of a body having an extended area surface, so as chemically to modify substantially said surface of said body.

Inventors: MACNICOL DAVID DEWAR, MACNICOL, DAVID, DEWAR
Applicants: UNIV DUNDEE, THE UNIVERSITY COURT OF THE UNIVERSITY OF GLASGOW
Application year: 1988
Main classification: C07C148
IPC codes: C07B31, C07B45, C07B61, C07C67, C07C313, C07C319, C07C321