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United States Patent (19) 11 Patent Number: 5,342,985 Herrmann Et Al

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United States Patent (19) 11 Patent Number: 5,342,985 Herrmann Et Al USOO5342985A United States Patent (19) 11 Patent Number: 5,342,985 Herrmann et al. (45. Date of Patent: Aug. 30, 1994 54) ORGANIC DERIVATIVES OF RHENIUM 58 Field of Search ................ 556/482, 485; 560/130, OXDES AND THER PREPARATION AND 560/219, 221, 205; 568/626, 627, 630, 655, 685, USE FOR THE METATHESS OF OLEFENS 687; 570/135, 136; 585/510,520 75 Inventors: Wolfgang A. Herrmann, Freising: Primary Examiner-Paul F. Shaver Werner Wagner, Munich; Ursula Attorney, Agent, or Firm-Connolly & Hutz Volkhardt, Freising, all of Fed. Rep. of Germany 57 ABSTRACT 73) Assignee: Hoechst AG, Frankfurt am Main, The invention relates to a process for the metathesis of Fed. Rep. of Germany olefins which comprises reacting an olefin of the for mula YCZ=CZ-(CX2),R2 (II) wherein 21 Appl. No.: 569,614 n is an integer from 1 to 28, 22 Filed: Aug. 20, 1990 X represents H or F, Y represents H or alkyl having from 1 to 10 carbon Related U.S. Application Data atoms and 63 Continuation-in-part of Ser. No. 320,404, Mar. 8, 1989, Z represents Hor a non-aromatic hydrocarbon group abandoned. having from 1 to 6 carbon atoms and R2 represents a H, alkyl, halogen, COOR3 or OR', wherein R3and 30 Foreign Application Priority Data R4 represent alkyl having from 1 to 15 carbon Dec. 10, 1988 DE Fed. Rep. of Germany ....... 384,733 atoms or phenyl which is unsubstituted or contains Jan. 31, 1989 IDE Fed. Rep. of Germany ....... 3902787 from 1 to 3 substituents or wherein R is trialkylsi Mar. 28, 1990 IDE Fed. Rep. of Germany ....... 4.00990 lyl RSi, wherein R5 represents alkyl having from 1 51l Int. Cl............................. CO7F 7/08; CO7F 7/18 to 5 carbon atoms, at a catalyst comprising an ox 52 U.S. C. .................................... 556/482; 556/485; idic carrier charged with a rhenium compound as 560/130,560/219;560/205; 560/221; 568/626; defined hereinbefore. 568/627; 568/630,568/655; 568/685; 568/687; 570/135; 570/136,585/510,585/520 17 Claims, 8 Drawing Sheets U.S. Patent Aug. 30, 1994 Sheet 1 of 8 5 9 342,985 fiul[][][]]/ fiulÇI |N133.10/[38] U.S. Patent Aug... 30, 1994 Sheet 3 of 8 5 342,985 001:1NIH}][]/[38] :N[3310 IWO U.S. Patent Aug 30 , 1994 Sheet 4 of 8 5 342,985 fiu0001/fiulGZ :N|J310 ;IVO U.S. Patent Aug... 30, 1994 Sheet 7 of 8 5 342,985 |N13310 5,342,985 1. 2 metathesis of derivatives of olefins, i.e. olefins contain ORGANIC DERVATIVES OF RHENUMOXDES ing heterofunctions, possible (K. J. Ivin: Olefin Metath AND THER PRE PARATION AND USE FOR THE esis, Academic Press, London 1983, 32-34). Thus the METATHESIS OF OLEFTNS metathesis of olefinically unsaturated carboxylic acid esters and of allyl halides and the like on multi-compo This application is a continuation-in-part of our ear nent catalysts, such as WCL6/Sn(CH3)4 or Re lier application Ser. No. 320,404 filed Mar. 8, 1989, now 2O7/Sn(CH3)4/Al2O3 has been described. The last abandoned. named system (R. A. Fridman et al., Dokl. Akad. Nauk. The present invention relates to organic derivatives SSSR 234, (1977), 1354–57; R. H. A. Bosma et al., J. of rhenium oxides and to their preparation and use for 10 Organometal. Chem. 225 (1983) 159-171; X. Xiaoding the metathesis of olefins as such and also derivatives of et al., J. Chem. Soc. Chem. Commun. 1985, 631-633; G. olefins. C. N. van den Aardweg, loc. cit. 1983, 262-263) is the The term metathesis designates, as is known, the only one containing rhenium which is capable of cleavage of olefinic compounds in such a way that the metathesizing olefinically unsaturated organic halides, double bond is broken apart and the two fragments 15 esters and the like. Hitherto there has been no knowl combine to form new compounds. In the wider sense, edge of the effective catalyst species. The following are metathesis also includes the ring-opening polymeriza practical disadvantages of the rhenium-containing cata tion of cycloolefins. In the specific case, where the said lyst systems hitherto used: cleavage is carried out in the presence of the basic olefin a) the necessity of using at the same time highly toxic ethylene, the reaction is a so-called ethenolytic metathe 20 tetraalkyltin compounds as activators in the me sis also called ethenolysis. In this reaction the double tathesis of derivatives of olefins (J. E. Cremer, bonds of the ethylene and of the other olefin are broken Biochem. J. 68 (1958) 685-688; W. N. Aldridge et apart and the resulting fragments combine in a statistical al., The Lancet, Sep. 26, 1981, page 692/3), manner to form new compounds. Where a symmetric b) low catalyst activity, inacceptable for industrial mono-olefin is subjected to a ethenolysis, only a single 25 use, and product is formed, while two different products are c) a breadth of application with relatively narrow formed if an unsymmetric mono-olefin is subjected to limits, i.e. the catalytic action is only found in the ethenolysis; when using di- or oligo-olefins, the number case of simple derivatives of olefins or olefins as of the final products is increased accordingly. Again, in such. a wider sense ethenolysis of olefins also includes the 30 It was therefore required to find a non-toxic and ring-opening of cyclo-olefins, in which case an co, co effective catalyst system which is as readily accessible, diolefin having n--2 chain links is formed from a cyclo simple to handle and stable on storage as possible and olefin having in chain links. which is also adequate without any activator in the As a result of the invention, an organorhenium com metathesis of olefin derivatives. Considerable interest pound of definite structure, which can be isolated in an 35 attaches to the industrial further processing of the prod undiluted form, becomes a catalyst for the first time. uctS. Ethenolytic cleavages of olefins are of commercial Although some so-called "organorhenium oxides', interest for the preparation of fine chemicals and bulk for example CH3ReO3, (m-Cs(CH3)5)ReO3 (= pen chemicals. Examples of the catalytic ethenolysis in in tamethylcyclopentadienylrhenium trioxide), are known dustry are the Phillips process for the preparation of 40 as catalyst components for the metathesis of olefins by 3,3-dimethyl-1-butene and the Shell process for the homogeneous catalysis W. A. Herrmann et al., Angew. preparation of co, co'-diolefins which compounds are of Chem. 100 (1988) 420-422, translation in Angew. industrial importance as crosslinking agents in the Chem. Int. Ed. Engl. 27 (1988) 394-396), the concomi polymerisation of olefins or for the preparation of bi tant use, as activator, of a Lewis acid which is at least functional compounds. 45 partially soluble in organic solvents was, however, al While it is the intention in the conventional metathe ways necessary, preferably aluminum(III) chloride and, sis of olefins, often called self-metathesis, to convert an in most cases, also the concomitant use of toxic tin tetra unsymmetric olefin in two other olefins having a alkyls (for example Sn(CH3)4) as further activators. shorter or longer chain of carbon atoms, or to polymer Even then the catalyst systems thus obtainable are com ise a cyclic olefin under ring-opening to yield a di- or 50 pletely inactive in respect of the metathesis of deriva higher polymerised product, the ethenolysis is distin tives of olefins. guished from such self-metathesis by the fact that al It has now been found, surprisingly, that methylr ways a-olefins are produced in which the fragments henium trioxide CH3ReO3 and related compounds of which are formed by the splitting of the double bond of the formula I indicated below are suitable for use as a the starting olefin are always prolonged by one CH2 55 metathesis catalyst when supported on oxide supporting group. Thus, the ethenolysis of olefins having non-ter materials, in particular aluminum oxide supports. The minal double bonds is the counter part of the self use of additional activator substances ("co-catalysts'), metathesis of a-olefins. which is disadvantageous for many reasons, thus be The ethenolysis is in fact always to be carried out comes superfluous for the first time. under elevated pressure and insofar it is somewhat dis The invention thus relates to the use of compounds of tinguished from the conventional metathesis of olefins rhenium which have the general formula RaRebOc (I) by its process conditions. Very often different catalysts in which a is 1 to 6, b is 1 to 4 and c is 1 to 14 and the are used for both kinds of metathesis. total of a, b and c is such that it accords with the pen It is known that compounds of the element rhenium tavalency to heptavalency of rhenium, subject to the exhibit catalytic activity in the metathesis of olefins, 65 proviso that not greater than 3Xb, and which are sup specifically only in the metathesis of olefins as such. ported on oxide supporting materials, as heterogeneous Only if so-called co-catalysts, in particular tetraalkyltin catalysts for metathesis. In this connection R. denotes compounds are added to such rhenium catalysts is the an organic group attached to the metal rhenium via a 5,342,985 3 4. carbon atom to which at least one hydrogen atom is still or different and can be hydrogen or alkyl having 1 to 4 attached, specifically alkyl radicals having to 9 carbon carbon atoms.
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