CA2079211C - Use of organic derivatives of rhenium oxides as catalysts for ethenolytic metathesis of olefinic compounds and process for ethenolytic metathesis of olefinic compounds using thesecatalysts - Google Patents
Use of organic derivatives of rhenium oxides as catalysts for ethenolytic metathesis of olefinic compounds and process for ethenolytic metathesis of olefinic compounds using thesecatalystsInfo
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Abstract
Use of compounds of formula R1aRebOc (I), in which a is 1 to 6, b is 1 to 4 and c is 1 to 14 and the sum of a, b and c is such that it satisfied rhenium in its 5- or 7- valency states, with the proviso that c is not greater than 3b, and in which R1 is an alkyl radical with 1 to 9 carbon atoms, a cycloalkyl radical with 5 to 10 carbon atoms or an aralkyl radical with 7 to 9 carbon atoms, where R1 may be at least partially fluorinated, the compounds do not contain more than three groups with more than 6 carbon atoms per rhenium atom and at least one hydrogen atom is bonded to the carbon atom in the .alpha.-position, which are applied to oxidic support materials, as catalysts for the ethenolytic metathesis of olefinic compounds.
Description
21~21 1 The present invention relates to a process for the so-called ethenolytic metathesis (ethenolysis) of non-functionalized and functionalized olefins using organic derivatives of rhenium oxides and to the use of such derivatives as catalyst~ for this ethenolysis.
The term ethenolysis describes the cleavage of olefinic compounds in the presence of the olefin parent substance ethylene, in such a way that the double bonds in the olefin concerned and in the ethylene are broken apart and the resulting fragments combine in a random fashion to give new olefinic compounds. Thus a single product is produced when a symmetric monoolefin is used. Two different products are obtained from an asymmetric monoolefin. The use of di- and oligoolefins increases the nllmher of products accordingly. Included in the ethenolysis of olefins in a wider sense is also the ring-opening of cycloolefins, an ~,~'-diolefin with n+2 chain members being obtained from a cycloolefin with n ring members.
For some time, ethenolytic olefin cleavages have been of industrial interest for the preparation of fine and large-scale chemicals. Thus the Phillips process for the preparation of neohexene (3,3-dimethyl-1-butene) and the Shell process for the preparation of ~,~'-diolefins, which are industrially important as cross-linking agents in olefin polymerization or for the preparation of bifunctional compounds, are examples from industry of catalytic olefin ethenolysis.
Whereas in conventional olefin metathesis, generally called "self-metathesis , the objective is to convert an asymmetric olefin into two other olefins with shorter or longer C-atom chains or to dimerize or polymerize a cyclic olefin by opening the ring, ethenolysis is differentiated from that to the extent that, basically, terminal olefins (~-olefins) are produced, the fragments CA 02079211 1998-0~-14 which are produced on cleaving the starting olefin at the double bond each being lengthened by a CH2 group. Ethenolysis of non-terminal olefins is therefore the counterpart of self-metathesis of ~-olefins.
Ethenolysis is virtually always a reaction which is carried out under pressure and also differs from conventional olefin metathesis with regard to process engineering. As a rule, different catalysts are also used for the two processes.
Surprisingly, it has now been found that compounds of general formula R1aRebOc (I), in which a is 1 to 6, b is 1 to 4 and c is 1 to 12 and the sum of a, b and c is such that it satisfies rhenium in its 5- or 7-valency states, with the proviso that c is not greater than 3b, and in which R1 is an alkyl radical with 1 to 9 carbon atoms, a cycloalkyl radical with 5 to 10 carbon atoms or an aralkyl radical with 7 to 9 carbon atoms, where R1 may be at least partially fluorinated, the compounds do not contain more than three groups with more than 6 carbon atoms per rhenium atom and at least one hydrogen atom is bonded to the carbon atom in the ~-position, which are applied to oxidic support materials, are suitable as catalysts (heterogeneous catalysts) for the ethenolysis (ethenolytic metathesis) of chain-like and cyclic, non-functionalized and functionalized olefins. When using these catalysts, the use of additional activators ("co-catalysts"), which is disadvantageous for many reasons, may in fact be dispensed with, this being required in older processes.
CA 02079211 1998-0~-14 - 2a -The invention also relates to a process for the ethenolysis of olefinic compounds, which is characterized in that non-funtionalized or funtionalized olefins of the type YCZ=CZ-(CX2)nR2 (II), in which n is an integer from 1 to 28, X
is H or F, Y is H or alkyl with 1 to 10 carbon atoms and Z is H or a non-aromatic hydrocarbon _ 3 20~9211 radical with 1 to 6 carbon atoms, Y and Z however not being hydrogen simultaneously, and the substituent RZ is H, alkyl, halogen, CoOR3 or oR4, in which R3 and R4 are alkyl with 1 to 15, preferably 1 to 6, carbon atoms or phenyl, which may also contain 1 to 3 substituents on the ring, or in which R4 is trialkylsilyl R53Si, in which R5 is alkyl with 1 to 5, preferably 1 to 3, carbon atoms, are reacted with ethylene on catalysts which comprise oxidic support materials onto which compounds of the aforementioned type are applied. When Z is different from H, it is preferably an open-chain alkyl with 1 to 4 carbon atoms. Z as alkyl is, for example, cyclohexyl, but is preferably an open-chain alkyl with 1 to 4 C-atoms.
When Z is phenyl, the substituents may be halogen, for example fluorine, chlorine or bromine, NO2, NR6R7, oR8 and/or alkyl. The radicals R6, R7 and R8 are the same or different and may be hydrogen or alkyl with 1 to 4 carbon atoms. R2 as halogen may be fluorine, chlorine, bromine or iodine. The two Zs may be the same or different. When Z
is hydrogen and R2 is halogen, this is preferably bromine.
Compounds in which at least one X = F are, for example, 1,6-di-(perfluoro-n-hexyl)-hex-3-ene of formula (n-C6F13)-CH2-CH2-CH=CH-CH2CH2-(n-C6F13) and perfluoropropene C3F6. The number n preferably varies within the range from 1 to 12 and in particular up to 8.
The catalysts are thus not only effective for olefins where Z = H but also for the ethenolysis of partially fluorinated olefins. They are also suitable for the ethenolysis of internal, functionalized olefins of formula R9CH=CH-(CH2)nR1~ (III), in which R9 is a branched or expediently non-branched alkyl radical with 1 to 12 carbon atoms, R10 is a carboxyalkyl radical, in which the alkyl radical expediently has 1 to 4 carbon atoms, and n is an integer from 1 to 10. Methyl oleate (R9 = n-octyl, R10 = CO2CH3, n = 7) may be mentioned as an example.
- 20792:11 The catalysts used according to the invention, however, not only catalyze the ethenolysis of open-chain compounds, but also the ring-opening ethenolysis of cycloolefins and cyclic hydrocarbons having several olefinic structural elements. Examples are cyclooctene, 1,5-cyclooctadiene and cycloolefins with up to 20 chain members, as well as cyclic di- and oligoolefins, which also carry functions contA; n ing hetero atoms.
In formula I, R1 represents an organic group which is bonded to the metal rhenium via a carbon atom to which at least one hydrogen atom is also bonded, to be precise alkyl radicals with 1 to 9 carbon atoms, cycloalkyl with 5 to 10 carbon atoms, such as cyclopentyl, cyclohexyl or l-norbornyl, or aralkyl with 7 to 9 carbon atoms, such as benzyl, but preferably methyl. The terms alkyl and cycloalkyl naturally mean that these groups contain no multiple bonds. For steric reasons, the presence of more than three groups with more than 6 carbon atoms per rhenium atom in the compounds is not possible; the compounds expediently contain at most only one such group. In this context, the term metathesis includes the ring-opening of cycloolefins.
Among compounds of formula I, CH3ReO3, (CH3)6Re2O3, (CH3)4Re2O4andpentamethylcyclopentadienylrheniumtrioxide are already known, but the catalytic effectiveness of these compounds in ethenolysis, i.e. in the reàction of ethylene under pressure, was not known and was as little to be expected as that of the whole class of compound~.
The catalytic effect is all the more surprising, as (trimethylstannoxy)rhenium trioxide t(CH3)3SnO]ReO3, which has an analogous structure, is just as catalytically ineffective as all other rhenium compounds containing oxygen, like dirhenium heptox;~P Re2O7, various perrhenates with the ~ReO4]~ anion, rhenium trioxide ReO3 and the other rhenium oxides Re2O5 and ReO2. (CH3)3SiOReO3 is also ineffective. In the compounds of formulae I and 207~211 II, alkyl is, for example, methyl, ethyl, propyl, isopropyl, the various butyl radicals such as n-, sec-, tert. and isobutyl, and the various pentyl, hexyl and octyl radicals, such as the 2-ethylhexyl radical.
The catalysts of the formula I used according to the present invention may be prepared in a very simple way from Re2O7 using the usual alkylating agents. Such alkylating agents are, for example, boron, aluminum, cadmium, mercury and in particular zinc and tin compounds. For example, dirhenium heptoxide is reacted in an anhydrous solvent which is inert towards rhenium compounds (e.g. tetrahydrofuran) at a temperature of -80 to +60aC, preferably -30 to +40~C, with a solution of Rl2Zn or of another alkylating agent, R1 having the above-mentioned meaning, the suspension produced in this way is filtered through an immersed frit and the volatile fractions are removed from the filtrate. When especially active zinc alkyls are reacted, it is recommended that the lower temperatures in the stated ranges are used in order to obtain selective reaction to give the desired rhenium compounds and thus to reduce or inhibit the formation of undesired by-products. In other cases, the prodcedure is advantageously carried out at from 0 to 60~C, preferably 10 to 40~C. The compounds of formula I
may be solids or liquids. Although they are as such insensitive to air and moisture, they should, however, be well dried before use. This also applies above all to the support materials.
Particularly suitable catalysts are those which contain methylrhenium trioxide CH3ReO3, which is readily available and is solid at room temperature, as the rhenium compound. Suitable support materials are in particular aluminum oxide and combinations thereof with silicon dioxide (e.g. SiO2/Al2O3 in a ratio by weight of 87:13), but also other oxides such as titanium, zirconium, niobium, tantalum and chromium oxides either on their own 20792ii or in combination with aluminum oxide and/or silicon dioxide. The aluminum oxide may be acidic, neutral or basic, depending on pretreatment. The activity of these catalysts may be raised considerably if the rhenium compounds are applied to a support, such as silica/aluminum oxide, from which water has been eliminated as far as possible by heating. If the support material does contain significant amounts of moisture, the activity is reduced because then the alkyl group bonded to the rhenium is sometimes abstracted by water as an alkane, e.g. according to the equation CH3ReO3 + H2O
CH4 + HReO4 Time- and energy-consuming operating steps may be dispensed with in the process according to the invention and yet very reproducible catalysts are obtained.
In the present process the catalytically active rhenium compound is applied to the catalyst support, advantageously silica gel/aluminum oxide, advantageously at room temperature, from a solvent, preferably a dichloromethane solution, the catalyst support simply being freed from moisture in a stream of nitrogen at 550 to 800~C for 2 hours before use, so that the catalyst system thereafter exhibits its full activity.
Care should be taken to exclude air and moisture during ethenolysis with the catalysts used according to the invention. Also, the olefins should expediently be thoroughly dried before use in order to avoid the formation of alkanes as by-products. The ethenolysis is in general performed at 3 to 30, preferably 5 to 20, bar pressure of ethylene and a temperature of -25 to +70~C, expediently +20 to 65~C.
The possibility of working under such relatively mild conditions is a particular advantage of the process according to the invention. However, it is also possible 2~792~
to use higher temperatures, for example up to 100~C, or to work at lower pressures, for example atmospheric pressure. However, there are usually no advantages associated with this.
Examples 1 to 13 - Ethenolysis using (CH3)ReO3 A solution of 13 mg (0.052 mmol) of methylrhenium trioxide, CH3ReO3, in 0.5 ml of dichloromethane was introduced into a suspension of 2000 mg of SiO2/AlzO3 catalyst support (ratio by weight 87:13, particle size less than 15~m, maintained at 550~C for 2 h) in 50 ml of dichloromethane (dried over calcium hydride and stored under an atmosphere of nitrogen) with stirring, in a 250 ml laboratory autoclave made from safety glass (BUCHI
glass reactor), at the temperature indicated in Table 1.
After 5 minutes' stirring, 2.5 mmol of olefin were injected (t = 0) and ethylene was injected to the pressure given in Table 1. After a reaction time of 5 h the products indicated in Table 1 were detected by gas chromatography in the liquid phase.
Examples 14 to 17 - Ethenolysis using (CH3)4RezO4 When this compound is used as catalyst for olefin metathesis, the same procedure was used as is described in Examples 1 to 13 for methylrhenium trioxide, CH3ReO3, except that instead of the solution of 13 mg of methylrhenium trioxide, a solution of 25.4 mg (0.052 mmol) of tetramethyltetraoxodirhenium, (CH3)4RezO4, in 0.5 ml of dichloromethane was introduced into a suspension of 2000 mg of the catalyst support. After a reaction time of 5 h, the products indicated in Tab. 2 were detected by gas chromatography in the li~uid phase.
207~
Table 1 Ethenolysis of non-functionalized and functionalized open-chain and cyclic olefins using (CH3)ReO3 Example/Starting Reaction Products Yields material conditions i!
(%) 1) cis/trans-3-heptene 10 bar/40~C l-butene 39 l-pentene 39 2) ~-di-iso-butene* 15 bar/40~C 3,3-dimethyl-l-butene 46 isobutene 45 3) 1,3-cyclohexadiene 8 bar/28~C 1,5-hexadiene 42 1,3-butadiene 40 1,4,7-octatriene 7 4) cyclododecene 8 bar/30~C 1,13-tetradeca-diene 98 5) cyclooctene 8 bar/30~C l,9-decadiene 91 6) 1,5-cyclooctadiene 15 bar/35~C 1,5-hexadiene 72 1,5,9-decatriene 12 7) cyclopentene 10 bar/28~C 1,6-heptadiene 80 8) l,9-cyclohexa- 15 bar/40~C 1,9,17-octadeca-decadiene triene 12 l,9-decadiene 66 9) ~,~'-diphenyl- 18 bar/65~C l,l-diphenyl-stilbene ethylene 53 10) 2-norbornene 13 bar/30~C 1,4-divinyl-cyclopentane 67 11) methyl oleate 15 bar/30~C l-decene 44 methyl 9-decenoate 46 12) ethyl linoleate 15 bar/40~C l-heptene 33 1,4-pentadiene 31 ethyl 9-decenoate 21 13) geranylacetone** 14 bar/-5~C isobutylene 33 2-methyl-1,5-hexadiene 28 4-(1-butenyl)-methyl ketone 29 ~V7g211L
* 2,4,4-trimethyl-2-pentene ** (cH3)2c-cH(cH2)2c(cH3)-cH(cH2)2c( o)cH3 a) Sum of the respective olefins corresponds to the conversion Table 2 Ethenolysis of olefins using (CH3)4Re204 on Al203/SiO2 Example/Starting Reaction ProductsYields material conditions (%) 14) cis/trans-3-heptene 10 bar/40~C l-butene 35 l-pentene 35 15) 1,3-cyclohexadiene 10 bar/30~C1,5-hexadiene 34 1,3-butadiene30 1,3,7-octatriene 10 16) cyclopentene 20 bar/30~C 1,6-heptadiene75 17) methyl oleate 15 bar/30~C l-decene 46 methyl 9-decenoate 44 a) Sum of the respective olefins corresponds to the conversion.
The term ethenolysis describes the cleavage of olefinic compounds in the presence of the olefin parent substance ethylene, in such a way that the double bonds in the olefin concerned and in the ethylene are broken apart and the resulting fragments combine in a random fashion to give new olefinic compounds. Thus a single product is produced when a symmetric monoolefin is used. Two different products are obtained from an asymmetric monoolefin. The use of di- and oligoolefins increases the nllmher of products accordingly. Included in the ethenolysis of olefins in a wider sense is also the ring-opening of cycloolefins, an ~,~'-diolefin with n+2 chain members being obtained from a cycloolefin with n ring members.
For some time, ethenolytic olefin cleavages have been of industrial interest for the preparation of fine and large-scale chemicals. Thus the Phillips process for the preparation of neohexene (3,3-dimethyl-1-butene) and the Shell process for the preparation of ~,~'-diolefins, which are industrially important as cross-linking agents in olefin polymerization or for the preparation of bifunctional compounds, are examples from industry of catalytic olefin ethenolysis.
Whereas in conventional olefin metathesis, generally called "self-metathesis , the objective is to convert an asymmetric olefin into two other olefins with shorter or longer C-atom chains or to dimerize or polymerize a cyclic olefin by opening the ring, ethenolysis is differentiated from that to the extent that, basically, terminal olefins (~-olefins) are produced, the fragments CA 02079211 1998-0~-14 which are produced on cleaving the starting olefin at the double bond each being lengthened by a CH2 group. Ethenolysis of non-terminal olefins is therefore the counterpart of self-metathesis of ~-olefins.
Ethenolysis is virtually always a reaction which is carried out under pressure and also differs from conventional olefin metathesis with regard to process engineering. As a rule, different catalysts are also used for the two processes.
Surprisingly, it has now been found that compounds of general formula R1aRebOc (I), in which a is 1 to 6, b is 1 to 4 and c is 1 to 12 and the sum of a, b and c is such that it satisfies rhenium in its 5- or 7-valency states, with the proviso that c is not greater than 3b, and in which R1 is an alkyl radical with 1 to 9 carbon atoms, a cycloalkyl radical with 5 to 10 carbon atoms or an aralkyl radical with 7 to 9 carbon atoms, where R1 may be at least partially fluorinated, the compounds do not contain more than three groups with more than 6 carbon atoms per rhenium atom and at least one hydrogen atom is bonded to the carbon atom in the ~-position, which are applied to oxidic support materials, are suitable as catalysts (heterogeneous catalysts) for the ethenolysis (ethenolytic metathesis) of chain-like and cyclic, non-functionalized and functionalized olefins. When using these catalysts, the use of additional activators ("co-catalysts"), which is disadvantageous for many reasons, may in fact be dispensed with, this being required in older processes.
CA 02079211 1998-0~-14 - 2a -The invention also relates to a process for the ethenolysis of olefinic compounds, which is characterized in that non-funtionalized or funtionalized olefins of the type YCZ=CZ-(CX2)nR2 (II), in which n is an integer from 1 to 28, X
is H or F, Y is H or alkyl with 1 to 10 carbon atoms and Z is H or a non-aromatic hydrocarbon _ 3 20~9211 radical with 1 to 6 carbon atoms, Y and Z however not being hydrogen simultaneously, and the substituent RZ is H, alkyl, halogen, CoOR3 or oR4, in which R3 and R4 are alkyl with 1 to 15, preferably 1 to 6, carbon atoms or phenyl, which may also contain 1 to 3 substituents on the ring, or in which R4 is trialkylsilyl R53Si, in which R5 is alkyl with 1 to 5, preferably 1 to 3, carbon atoms, are reacted with ethylene on catalysts which comprise oxidic support materials onto which compounds of the aforementioned type are applied. When Z is different from H, it is preferably an open-chain alkyl with 1 to 4 carbon atoms. Z as alkyl is, for example, cyclohexyl, but is preferably an open-chain alkyl with 1 to 4 C-atoms.
When Z is phenyl, the substituents may be halogen, for example fluorine, chlorine or bromine, NO2, NR6R7, oR8 and/or alkyl. The radicals R6, R7 and R8 are the same or different and may be hydrogen or alkyl with 1 to 4 carbon atoms. R2 as halogen may be fluorine, chlorine, bromine or iodine. The two Zs may be the same or different. When Z
is hydrogen and R2 is halogen, this is preferably bromine.
Compounds in which at least one X = F are, for example, 1,6-di-(perfluoro-n-hexyl)-hex-3-ene of formula (n-C6F13)-CH2-CH2-CH=CH-CH2CH2-(n-C6F13) and perfluoropropene C3F6. The number n preferably varies within the range from 1 to 12 and in particular up to 8.
The catalysts are thus not only effective for olefins where Z = H but also for the ethenolysis of partially fluorinated olefins. They are also suitable for the ethenolysis of internal, functionalized olefins of formula R9CH=CH-(CH2)nR1~ (III), in which R9 is a branched or expediently non-branched alkyl radical with 1 to 12 carbon atoms, R10 is a carboxyalkyl radical, in which the alkyl radical expediently has 1 to 4 carbon atoms, and n is an integer from 1 to 10. Methyl oleate (R9 = n-octyl, R10 = CO2CH3, n = 7) may be mentioned as an example.
- 20792:11 The catalysts used according to the invention, however, not only catalyze the ethenolysis of open-chain compounds, but also the ring-opening ethenolysis of cycloolefins and cyclic hydrocarbons having several olefinic structural elements. Examples are cyclooctene, 1,5-cyclooctadiene and cycloolefins with up to 20 chain members, as well as cyclic di- and oligoolefins, which also carry functions contA; n ing hetero atoms.
In formula I, R1 represents an organic group which is bonded to the metal rhenium via a carbon atom to which at least one hydrogen atom is also bonded, to be precise alkyl radicals with 1 to 9 carbon atoms, cycloalkyl with 5 to 10 carbon atoms, such as cyclopentyl, cyclohexyl or l-norbornyl, or aralkyl with 7 to 9 carbon atoms, such as benzyl, but preferably methyl. The terms alkyl and cycloalkyl naturally mean that these groups contain no multiple bonds. For steric reasons, the presence of more than three groups with more than 6 carbon atoms per rhenium atom in the compounds is not possible; the compounds expediently contain at most only one such group. In this context, the term metathesis includes the ring-opening of cycloolefins.
Among compounds of formula I, CH3ReO3, (CH3)6Re2O3, (CH3)4Re2O4andpentamethylcyclopentadienylrheniumtrioxide are already known, but the catalytic effectiveness of these compounds in ethenolysis, i.e. in the reàction of ethylene under pressure, was not known and was as little to be expected as that of the whole class of compound~.
The catalytic effect is all the more surprising, as (trimethylstannoxy)rhenium trioxide t(CH3)3SnO]ReO3, which has an analogous structure, is just as catalytically ineffective as all other rhenium compounds containing oxygen, like dirhenium heptox;~P Re2O7, various perrhenates with the ~ReO4]~ anion, rhenium trioxide ReO3 and the other rhenium oxides Re2O5 and ReO2. (CH3)3SiOReO3 is also ineffective. In the compounds of formulae I and 207~211 II, alkyl is, for example, methyl, ethyl, propyl, isopropyl, the various butyl radicals such as n-, sec-, tert. and isobutyl, and the various pentyl, hexyl and octyl radicals, such as the 2-ethylhexyl radical.
The catalysts of the formula I used according to the present invention may be prepared in a very simple way from Re2O7 using the usual alkylating agents. Such alkylating agents are, for example, boron, aluminum, cadmium, mercury and in particular zinc and tin compounds. For example, dirhenium heptoxide is reacted in an anhydrous solvent which is inert towards rhenium compounds (e.g. tetrahydrofuran) at a temperature of -80 to +60aC, preferably -30 to +40~C, with a solution of Rl2Zn or of another alkylating agent, R1 having the above-mentioned meaning, the suspension produced in this way is filtered through an immersed frit and the volatile fractions are removed from the filtrate. When especially active zinc alkyls are reacted, it is recommended that the lower temperatures in the stated ranges are used in order to obtain selective reaction to give the desired rhenium compounds and thus to reduce or inhibit the formation of undesired by-products. In other cases, the prodcedure is advantageously carried out at from 0 to 60~C, preferably 10 to 40~C. The compounds of formula I
may be solids or liquids. Although they are as such insensitive to air and moisture, they should, however, be well dried before use. This also applies above all to the support materials.
Particularly suitable catalysts are those which contain methylrhenium trioxide CH3ReO3, which is readily available and is solid at room temperature, as the rhenium compound. Suitable support materials are in particular aluminum oxide and combinations thereof with silicon dioxide (e.g. SiO2/Al2O3 in a ratio by weight of 87:13), but also other oxides such as titanium, zirconium, niobium, tantalum and chromium oxides either on their own 20792ii or in combination with aluminum oxide and/or silicon dioxide. The aluminum oxide may be acidic, neutral or basic, depending on pretreatment. The activity of these catalysts may be raised considerably if the rhenium compounds are applied to a support, such as silica/aluminum oxide, from which water has been eliminated as far as possible by heating. If the support material does contain significant amounts of moisture, the activity is reduced because then the alkyl group bonded to the rhenium is sometimes abstracted by water as an alkane, e.g. according to the equation CH3ReO3 + H2O
CH4 + HReO4 Time- and energy-consuming operating steps may be dispensed with in the process according to the invention and yet very reproducible catalysts are obtained.
In the present process the catalytically active rhenium compound is applied to the catalyst support, advantageously silica gel/aluminum oxide, advantageously at room temperature, from a solvent, preferably a dichloromethane solution, the catalyst support simply being freed from moisture in a stream of nitrogen at 550 to 800~C for 2 hours before use, so that the catalyst system thereafter exhibits its full activity.
Care should be taken to exclude air and moisture during ethenolysis with the catalysts used according to the invention. Also, the olefins should expediently be thoroughly dried before use in order to avoid the formation of alkanes as by-products. The ethenolysis is in general performed at 3 to 30, preferably 5 to 20, bar pressure of ethylene and a temperature of -25 to +70~C, expediently +20 to 65~C.
The possibility of working under such relatively mild conditions is a particular advantage of the process according to the invention. However, it is also possible 2~792~
to use higher temperatures, for example up to 100~C, or to work at lower pressures, for example atmospheric pressure. However, there are usually no advantages associated with this.
Examples 1 to 13 - Ethenolysis using (CH3)ReO3 A solution of 13 mg (0.052 mmol) of methylrhenium trioxide, CH3ReO3, in 0.5 ml of dichloromethane was introduced into a suspension of 2000 mg of SiO2/AlzO3 catalyst support (ratio by weight 87:13, particle size less than 15~m, maintained at 550~C for 2 h) in 50 ml of dichloromethane (dried over calcium hydride and stored under an atmosphere of nitrogen) with stirring, in a 250 ml laboratory autoclave made from safety glass (BUCHI
glass reactor), at the temperature indicated in Table 1.
After 5 minutes' stirring, 2.5 mmol of olefin were injected (t = 0) and ethylene was injected to the pressure given in Table 1. After a reaction time of 5 h the products indicated in Table 1 were detected by gas chromatography in the liquid phase.
Examples 14 to 17 - Ethenolysis using (CH3)4RezO4 When this compound is used as catalyst for olefin metathesis, the same procedure was used as is described in Examples 1 to 13 for methylrhenium trioxide, CH3ReO3, except that instead of the solution of 13 mg of methylrhenium trioxide, a solution of 25.4 mg (0.052 mmol) of tetramethyltetraoxodirhenium, (CH3)4RezO4, in 0.5 ml of dichloromethane was introduced into a suspension of 2000 mg of the catalyst support. After a reaction time of 5 h, the products indicated in Tab. 2 were detected by gas chromatography in the li~uid phase.
207~
Table 1 Ethenolysis of non-functionalized and functionalized open-chain and cyclic olefins using (CH3)ReO3 Example/Starting Reaction Products Yields material conditions i!
(%) 1) cis/trans-3-heptene 10 bar/40~C l-butene 39 l-pentene 39 2) ~-di-iso-butene* 15 bar/40~C 3,3-dimethyl-l-butene 46 isobutene 45 3) 1,3-cyclohexadiene 8 bar/28~C 1,5-hexadiene 42 1,3-butadiene 40 1,4,7-octatriene 7 4) cyclododecene 8 bar/30~C 1,13-tetradeca-diene 98 5) cyclooctene 8 bar/30~C l,9-decadiene 91 6) 1,5-cyclooctadiene 15 bar/35~C 1,5-hexadiene 72 1,5,9-decatriene 12 7) cyclopentene 10 bar/28~C 1,6-heptadiene 80 8) l,9-cyclohexa- 15 bar/40~C 1,9,17-octadeca-decadiene triene 12 l,9-decadiene 66 9) ~,~'-diphenyl- 18 bar/65~C l,l-diphenyl-stilbene ethylene 53 10) 2-norbornene 13 bar/30~C 1,4-divinyl-cyclopentane 67 11) methyl oleate 15 bar/30~C l-decene 44 methyl 9-decenoate 46 12) ethyl linoleate 15 bar/40~C l-heptene 33 1,4-pentadiene 31 ethyl 9-decenoate 21 13) geranylacetone** 14 bar/-5~C isobutylene 33 2-methyl-1,5-hexadiene 28 4-(1-butenyl)-methyl ketone 29 ~V7g211L
* 2,4,4-trimethyl-2-pentene ** (cH3)2c-cH(cH2)2c(cH3)-cH(cH2)2c( o)cH3 a) Sum of the respective olefins corresponds to the conversion Table 2 Ethenolysis of olefins using (CH3)4Re204 on Al203/SiO2 Example/Starting Reaction ProductsYields material conditions (%) 14) cis/trans-3-heptene 10 bar/40~C l-butene 35 l-pentene 35 15) 1,3-cyclohexadiene 10 bar/30~C1,5-hexadiene 34 1,3-butadiene30 1,3,7-octatriene 10 16) cyclopentene 20 bar/30~C 1,6-heptadiene75 17) methyl oleate 15 bar/30~C l-decene 46 methyl 9-decenoate 44 a) Sum of the respective olefins corresponds to the conversion.
Claims (18)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A process for preparing a catalyst for the ethenolytic metathesis of an olefinic compound which process comprises applying to an oxidic support material a compound of general formula R1aRebOc (I), in which a is 1 to 6, b is 1 to 4 and c is 1 to 12 and the sum of a, b and c is such that it satisfies rhenium in its 5- or 7-valency states, with the proviso that c is not greater than 3b, and in which R1 is an alkyl radical with 1 to 9 carbon atoms, a cycloalkyl radical with 5 to 10 carbon atoms or an aralkyl radical with 7 to 9 carbon atoms, where R1 may be at least partially fluorinated, said compound does not contain more than three groups with more than 6 carbon atoms per rhenium atom and at least one hydrogen atom is bonded to the carbon atom in the .alpha.-position.
2. A process for the ethenolytic metathesis of an olefinic compound, characterized in that an olefin of the type YCZ=CZ-(CX2)nR2 (II), in which n is an integer from 1 to 28, X
is H or F, Y is H or alkyl with 1 to 10 carbon atoms and Z is H or a non-aromatic hydrocarbon radical with 1 to 6 carbon atoms, Y and Z however not being hydrogen simultaneously, and the substituent R2 is H, alkyl, halogen, COOR3 or OR4, in which R3 and R4 are alkyl with 1 to 15 carbon atoms or phenyl, which may also contain 1 to 3 substituents on the ring, or in which R4 is trialkylsilyl R5 3Si, in which R5 is alkyl with 1 to 5 carbon atoms, is reacted with ethylene on a catalyst which comprises an oxidic support material onto which a rhenium compound of the type defined in Claim 1 has been applied.
is H or F, Y is H or alkyl with 1 to 10 carbon atoms and Z is H or a non-aromatic hydrocarbon radical with 1 to 6 carbon atoms, Y and Z however not being hydrogen simultaneously, and the substituent R2 is H, alkyl, halogen, COOR3 or OR4, in which R3 and R4 are alkyl with 1 to 15 carbon atoms or phenyl, which may also contain 1 to 3 substituents on the ring, or in which R4 is trialkylsilyl R5 3Si, in which R5 is alkyl with 1 to 5 carbon atoms, is reacted with ethylene on a catalyst which comprises an oxidic support material onto which a rhenium compound of the type defined in Claim 1 has been applied.
3. A process according to claim 2 in which R3 and R4 are alkyl with 1 to 6 carbon atoms and R5 is alkyl with 1 to 3 carbon atoms.
4. A process according to Claim 2, characterized in that the catalyst support essentially comprises aluminum oxide, silicon dioxide or a titanium, zirconium, niobium, tantalum or chromium oxide or a combination of said oxides.
5. Process according to Claim 2, 3 or 4, wherein the process is effected at a pressure of 3 to 30, bar of ethylene.
6. Process according to Claim 2, 3 or 4, wherein the process is effected at a pressure of 5 to 20, bar of ethylene.
7. A process according to Claim 5, wherein the process is effected at a temperature of -25 to +70°C.
8. A process according to Claim 6, wherein the process is effected at a temperature of +20 to +65°C.
9. A process according to Claim 2, 3 or 4, wherein the olefin of formula II is a cycloolefin.
207921 !
207921 !
10. A process according to Claim 8, wherein the olefin of formula II is a cycloolefin.
11. A process according to Claim 2, 3 or 4, wherein the olefin of formula II is a functionalized olefin.
12. A process according to Claim 8, wherein the olefin of formula II is a functionalized olefin.
13. A process according to Claim 2, 3 or 4, wherein R4 is alkyl with 1 to 6 carbon atoms.
14. A process according to Claim 8, wherein R4 is alkyl with 1 to 6 carbon atoms.
15. A process according to Claim 2, 3 or 4, wherein R5 is alkyl with 1 to 3 carbon atoms.
16. A process according to Claim 8, wherein R5 is alkyl with 1 to 3 carbon atoms.
17. A process according to Claim 1, 2, 3 or 4, wherein the active component in formula I is methylrhenium trioxide CH3ReO3.
18. A process according to Claim 8, wherein the active component in formula I is methylrhenium trioxide CH3ReO3.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE4009910A DE4009910A1 (en) | 1988-12-10 | 1990-03-28 | Ethenolytic metathesis of olefin(s) - using organo-rhenium oxide catalyst on oxidic carrier |
| DEP4009910.5 | 1990-03-28 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CA2079211A1 CA2079211A1 (en) | 1991-09-29 |
| CA2079211C true CA2079211C (en) | 1998-09-22 |
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| Application Number | Title | Priority Date | Filing Date |
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| CA002079211A Expired - Fee Related CA2079211C (en) | 1990-03-28 | 1991-03-20 | Use of organic derivatives of rhenium oxides as catalysts for ethenolytic metathesis of olefinic compounds and process for ethenolytic metathesis of olefinic compounds using thesecatalysts |
Country Status (5)
| Country | Link |
|---|---|
| EP (1) | EP0522067B1 (en) |
| JP (1) | JPH0776184B2 (en) |
| CA (1) | CA2079211C (en) |
| DE (1) | DE59105881D1 (en) |
| WO (1) | WO1991014665A1 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| FR2726488B1 (en) | 1994-11-04 | 1996-12-13 | Inst Francais Du Petrole | NOVEL SUPPORTED CATALYSTS CONTAINING RHENIUM AND ALUMINUM, THEIR PREPARATION AND THEIR USE FOR OLEFIN METATHESIS |
| EP0975622B1 (en) * | 1997-04-18 | 2002-10-09 | Studiengesellschaft Kohle mbH | Selective olefin metathesis of bifunctional or polyfunctional substrates in compressed carbon dioxide as reaction medium |
| KR100869981B1 (en) | 2001-03-26 | 2008-11-24 | 다우 글로벌 테크놀로지스 인크. | Metathesis of unsaturated fatty acid esters or unsaturated fatty acids with lower olefins |
| US7576227B2 (en) | 2002-04-29 | 2009-08-18 | Union Carbide Chemicals & Plastics Technology Corporation | Integrate chemical processes for industrial utilization of seed oils |
| US7002049B2 (en) | 2002-08-19 | 2006-02-21 | Eastman Chemical Company | Process for α,β-dihydroxyalkenes and derivatives |
| BRPI0415176B1 (en) | 2003-10-09 | 2014-04-15 | Dow Global Technologies Llc | Process of preparation of an unsaturated alcohol and composition |
| DE502005002564D1 (en) * | 2005-02-22 | 2008-03-06 | Miltitz Aromatics Gmbh | Method and apparatus for conducting a ring-opening cross-metathesis reaction between cyclic and acyclic olefins |
| EP1896385B1 (en) * | 2005-06-06 | 2013-08-28 | Dow Global Technologies LLC | Metathesis process for preparing an alpha, omega -functionalized olefin |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3776973A (en) * | 1967-05-03 | 1973-12-04 | Phillips Petroleum Co | Olefin conversion using complexes of mn,tc,and re with organoaluminum |
| US4180524A (en) * | 1978-02-16 | 1979-12-25 | Phillips Petroleum Company | Disproportionation/double-bond isomerization of olefins |
| FR2499083B1 (en) * | 1981-02-04 | 1986-02-21 | Rhone Poulenc Chim Base | NOVEL OXO COMPLEXES OF TRANSITIONAL METALS COORDINATED WITH LEWIS ACID - PROCESS FOR THE PREPARATION OF SUCH COMPLEXES - USE OF THESE COMPLEXES AS CATALYSTS IN THE REACTION OF METATHESIS OF OLEFINS |
| CA1330566C (en) * | 1988-12-10 | 1994-07-05 | Wolfgang Anton Herrmann | Organic derivatives of rhenium oxides and their preparation and use for the metathesis of olefins |
-
1991
- 1991-03-20 EP EP91907710A patent/EP0522067B1/en not_active Expired - Lifetime
- 1991-03-20 DE DE59105881T patent/DE59105881D1/en not_active Expired - Fee Related
- 1991-03-20 WO PCT/EP1991/000543 patent/WO1991014665A1/en active IP Right Grant
- 1991-03-20 JP JP3507471A patent/JPH0776184B2/en not_active Expired - Fee Related
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Also Published As
| Publication number | Publication date |
|---|---|
| JPH0776184B2 (en) | 1995-08-16 |
| JPH05506219A (en) | 1993-09-16 |
| WO1991014665A1 (en) | 1991-10-03 |
| CA2079211A1 (en) | 1991-09-29 |
| EP0522067A1 (en) | 1993-01-13 |
| DE59105881D1 (en) | 1995-08-03 |
| EP0522067B1 (en) | 1995-06-28 |
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