WO1991003449A1

WO1991003449A1 - Isomerization of alk-2-enyl ethers

Info

Publication number: WO1991003449A1
Application number: PCT/US1990/004323
Authority: WO
Inventors: Jeffrey S. Plotkin
Original assignee: Gaf Chemicals Corporation
Priority date: 1989-09-05
Filing date: 1990-08-06
Publication date: 1991-03-21
Also published as: AU6152090A; CA2023565A1

Abstract

This invention is directed to a process for the isomerization of alk-2-enyl ethers to the corresponding alk-1-enyl ethers under anhydrous conditions by the use of a supported rare metal catalyst atomic number 44 or 45 which comprises contacting the allyl ether with between about 0.1 and about 20 wt. % of said supported catalyst in which the amount of rare metal with respect to support is between about 0.05 and about 10 wt. %.

Description

ISOMERIZATION OF ALK-2-ENYL ETHERS

In one aspect the present invention relates to a novel process for converting allyl ethers to propenyl ethers in high yield.

In another aspect the invention relates to a nov composition comprising a mixture of an allyl ether and a selective supported transition metal catalyst.

BACKGROUND OF THE INVENTION

As pointed out in the Journal of the Chemical Society, 1980, Chemical Communications, pages 980-981, th preparation of vinyl ethers has become important both in terms of the synthetic use of the aliphatic Claisen rearrangement, and in the use of metallated derivatives o vinyl ether as masked acyl equivalents. In the carbohydrate field, allyl ethers have been used as selective protecting groups for alcohols; however, the first step in their removal generally requires isomerization to the vinyl ether followed by hydrolysis. Several soluble transition metal catalysts have been foun to accomplish this isomerization as referenced in NEW PATHWAYS FOR ORGANIC SYNTHESIS, Plenum Press, 1984, pages 179-181. The heterogeneous isomerization catalyst disclosed in the Journal of the Chemical Society [ibid] i palladium on charcoal; although heterogeneous catalysts a preferred for commercial applications, it has been found that this catalyst's activity is too low for commercial use. Specifically in some cases, the use of supported palladium achieves only 40% conversion after 20 hours of contact. Consequently, the resulting product mixture contains substantial amounts of the non-converted, non-hydrolyzable allyl ether component. Other advantages of the vinyl or prop-1-enyl ethers is that they can be cured instantaneously by radiation in the presence of a photoinitiatbr, whereas the allyl form has poor curing properties and remains tacky over long periods of time. Further, the prop-1-enyl isomer, in contrast with the allyl form, is copolymerizable with electron deficient olefins. These and many other additional advantages contribute to the importance of a process which selectively converts allyl ethers to their corresponding prop-l-enyl ether isomer in high yield.

Accordingly, it is an object of this invention to provide an economical and commercially feasible process for achieving greater than 90% conversion of an alk-2-enyl ether to its corresponding alk-l-enyl ether isomer.

Another object of the invention is to provide a highly reactive heterogeneous alk-2-enyl ether-catalyst composition which allows for product recovery by filtration.

Still another object is to provide alk-l-enyl ether products in substantial purity which can be cured instantaneously by irradiation.

Yet another object is to provide an alk-2-enyl isomerization catalyst which is markedly more economical than the current palladium catalyst.

These and other objects of the invention will become apparent from the following description and disclosure.

THE INVENTION

In accordance with this invention there is provided a supported rare metal catalyst of atomic number '44 or 45 which has the capability of converting a compound having a functional alk-2-enyl ether group (e.g. an allyl ether group) to the corresponding alk-l-enyl ether isomer in high yield and selectivity. The catalyst consists essentially of between about 0.05 and about 10 wt. %, preferably from about 0.1 to about 5 wt. % rare metal on support such as carbon, alumina, silica, silica/alumina, magnesia or a mixture thereof. Of these catalysts, ruthenium on alumina or other supports is preferred for i significantly higher conversion within a shorter reaction period. The isomerization reaction employs between about 0.1 and about 20 wt. %, preferably between about 0.5 and about 5 wt. % of the supported catalyst based on alk-2-en ether.

As stated above the present process applies to a alk-2-enyl ether. Accordingly suitable alk-2-enyl ethers include mono- and di- allyl ethers; a mono-, di-, tri-, tetra-, penta- or hexa- allyl ether alkane; the allyl eth of a tri ethylol alkane, glycerol, cellulose, alkoxylated cellulose, starch, or a sugar such as sucrose, glucose, etc; aryl substituted with from 1 to 6 prop-2-enyloxy carboxylate groups, e.g.

wherein A is lower alkylene; and ethers having the formul

wherein R' is hydrogen or a radical having from 1 to 20 carbon atoms and is selected from the group of aryl, alkaryl, aralkyl, alkyl and alkoxy or R', together with t oxygen atom of. the -CH=CY-CH₂0- moiety, forms a 4 to 6 membered heterocyclic ring; Y is hydrogen or lower alkyl; has a value of from 0 to 50; Z is an aliphatic radical having from 2 to 10 carbon atoms and is selected from the group of alkylene, alkenylene, alkynylene, alkyleneoxy, carboxylate and aminocarboxylate; x has a value consisten with the free valences in R; and R is hydrogen or a mono or poly valent radical having from 1 to 20 carbon atoms or a polymer thereof and is an aliphatic radical of the group of alkylene, alkenylene, alkynylene, alkarylene, an aromatic radical of the group of phenylene, tolylene, or xylylene, which radicals are optionally substituted with halo, lower alkyl, lower alkylene, hydroxyalkyl, alkenyloxy, alkoxy, alkylcarbonyl, alkenyl or alkenylcarbonyl; a divalent 3 to 6 membered heterocyclic radical having S, O or N as the hetero atom; or the radical

and alkoxylated derivatives thereof wherein v has a value of from 1 to 50; A is halo, lower alkyl, lower alkoxy or hydroxy; m has a value of from 0 to 2; p has a value of from 0 to 1 and R" is lower alkylene, sulfone, sulfur or oxygen.

In the above formula it is to be understood that the alkyl, alkenyl and alkylene groups can be linear or branched in structure. Examples of specific alk-2-enyl ethers which can be employed include allyl vinyl ether, hexyl allyl ether, octyl allyl ether, dodecyl allyl ether, phenyl allyl ether, diallyl ether, tetraallyloxymethyl methane, triallyloxy methyl ethane, triallyloxymethyl propane, hexaallyloxy methyl hexane, tetraallyloxy methyl butane, thiocyclopropyl allyl ether, tetrahydrofuran-3-yl allyl ether, but-2-enyl allyl ether, dihex-2-enyl ether. di-dodec-2-enyl ether, dibut-2-enyl ether, tetrahydrothiophene-3-yl allyl ether, hexahydropyran-2-yl allyl ether, hexahydrothiopyran-2-yl allyl ether, 4-allyloxy-2-butanone, di(phenylallyl) ether, the diallyl ether of bisphenols, e.g. the diallyl ether of bisphenol A the diallyl ether of alkoxylated bisphenols, di(allyloxyalkyl) benzene dicarboxylate, di(allyloxyalkyl) toluene, di(allyloxyalkyl) xylene, diaminocarboxylate, allyloxybenzyl polymer, l-allyloxy-5-hexen-2-one, (cyclohexenyl methyl)butyl ether, (3-phenyl prop-2-enyl) ethyl ether, (5-methyl-oct-2-enyl) methyl ether, diallylox cellulose, dodec-2-enyl butyl ether, the allyl ether of th onomethyl ether of triethylene glycol having the formula

CH₂=CHCH₂0(C₂H₄0)3CH₃

the alkoxylates of allyl alcohol having the formula CH₂=CHCH₂0 (alkyleneoxy)_nH wherein n has a value of from 1 to 50, the diallyl ether of triethylene glycol having the formula

CH₂=CHCH₂0(CH₂CH₂0)₃CH₂CH=CH₂

allyl glycidyl ether having the formula

O

CH₂=CHCH₂OCH₂-CH-CH₂ ,

and ethoxylated and/or propoxylated derivatives thereof. Preferred alk-2-enyl ethers are diallyl ether and pol alk-2-enyl ethers wherein R¹ is hydrogen or lower alkyl and Y is hydrogen or lower alkylene, n has a value of from 0 to 10; x has a value of from 1 to 6 and R is alkylene, alkoxylated alkylene, polyalkyleneoxy, a divalent heterocyclic moiety or 2,2-diphenyloxy-propane. Host preferred of the alk-2-enyl ethers are those of the formula

R^«CH₂CH=CR^« • ^,0(B)_wCH=CR' • ^,CH₂R'

wherein R* is hydrogen or a radical having from 1 to 20 carbon atoms and is selected from the group of aryl, e.g. phenyl, alkaryl e.g. tolylyl or xylyl, alkyl and alkoxy; R* • • is hydrogen or lower alkyl; B is alkyleneoxy having from 2 to 4 carbon atoms and w has a value of from 3 to 10.

It has been found that the compounds containing heterocyclic or cyclic R groups undergo isomerization by the present process in the absence of ring opening so that the corresponding isomeric product is obtained.

The allyl ethers employed herein vary widely in molecular weight, e.g. between about 100 up to about 1,000,000. As indicated above, the R and R' groups can be branched, linear or cyclic in structure.

The isomerization process comprises contacting the catalyst and alk-2-enyl ether under anhydrous conditions until a uniform heterogeneous mixture is obtained and reacting the mixture at a temperature of from about 60° to about 200°C. under a pressure of from about 14 to about 500 psig for a period of between about 2 hours and about 14 days; however, under preferred conditions, a temperature between about 100° and about 160°C. ; a pressure between about 14 and about 50 psig and a reaction time of from about 4 to about 48 hours, is employed. The reaction can be effected in dry air or under an inert gas, nitrogen being preferred. The isomerization reaction involving a dialk-2-enyl ether as representative of the various types included in this invention is illustrated by the followin equation:

R^»CH=CY-CH₂0-(ZO) R + catalyst-

The products of the present process are obtained as a mixture of cis and trans forms in a ratio which can vary between about 5:1 and about 1:5 depending upon the reaction temperature. It is found that higher temperatur within the above range favor the trans isomeric form.

Certain polyalkoxylated alk-l-enyl ether product i.e.

wherein R¹ is as defined above, B is C₂ to C₄ alkyleneoxy of branched or linear structure and w is 3-50, preferably 3-10, ^'which products are derived from the corresponding alk-2-enyl ether reactants disclosed herein, have the ability to solubilize photoinitiators which the corresponding alk-l-enyl ethers containing less than 3 alkyleneoxy grou lack. This property together with their low viscosities and low volatilities is particularly important for diluen employed in radiation curable coating resins.

As stated above the process of the present invention is effected by contacting the supported transition metal with the allyl ether at elevated temperature for a period sufficient to complete the reaction. Lower molecular weight non-viscous allyl ether can be directly contacted with the supported catalyst. However, where viscous or solid allyl ethers are employed an inert liquid diluent having a reflux temperature below the isomeric product is recommended. Suitable solvents include xylene, toluene, dimethoxy ethane, ketones, ethers, e.g. methoxy ethyl ether and esters. The use of solvent is not restricted to highly viscous ethers and may be employed when desired in concentrations up to about 90 wt. %.

The method of contacting the alk-2-enyl ether and catalyst can be effected by any conventional process; however, passing the alk-2-enyl ether over a fixed bed of granular or pelletized catalyst or slurrying the alk-2-enyl ether and powdered catalyst are preferred. In a fixed bed operation, the liquid product, is continuously recovered from the reactor. Alternatively the liquid reaction product can be recycled to the fixed bed reactor for additional conversion to product, when desired. When a slurry is employed, the resulting product mixture is filtered to remove catalyst and, in cases where an inert diluent is employed, the remaining liquid mixture is heated to distill off the solvent and to separate the isomeric product. If desired, the remaining liquid product can be fractionally distilled; however, such purification is generally not required since the product is obtained in substantially high purity, eg. greater than 90% The separated catalyst can be directly recycled to the reaction zone, needing no purification or activation.

Reactions with the ruthenium catalyst achieve greater than 98% conversion at completion and about 80% conversion is realized within the first 3-5 hours of contact. Figure 1 presents a diagrammatic comparison of the present catalyst with a supported palladium catalyst described by H. Carless and David Haywood in the Journal of Chemical Society, Chemical Communications, 1980 pp. 980-981. It is found that the reaction with supported ruthenium achieves an overall 2.5-fold improvement in conversion to desired isomer and greater than a 3-fold improvement in conversion within the first 4 hours of operation. Having generally described the invention, reference is now had to the accompanying examples which se forth preferred embodiments of the invention and comparative data, but which are not to be construed as limiting to the invention as more broadly disclosed above and in the appended claims.

EXAMPLES 1-4

Several supported transition metals, shown in the following Table were slurried with octyl allyl ether at 140°C. for 20 hours under ambient pressure of dry nitroge gas.

In each experiment, a 2 wt. % catalyst concentration was employed and the catalysts comprised 5% transition metal on the designated support. After completion of the reaction, the respective mixtures were separately filtered and analyzed by gas chromotography fo selective conversion to the corresponding octyl prop-1-en ether product. The results are reported as follows.

Catalyst % Conversion

Ru/Al₂0₃ >99%

Ru/Carbon >99%

*Pd/Carbon 39%

Pd/Al₂0₃ 44%

* catalyst reported by H.A.J. Carless and David J. Haywo in the Journal of the Chemical Society, [ibid]. EXAMPLES 5 & 6

Example 1 was repeated except that the allyl ether of the monomethyl ether of triethylene glycol was substituted for octyl allyl ether. The results of these experiments are those plotted on the graph of Figure 1.

EXAMPLE 7

In a glass 3-necked flask 500 grams of allyl glycidyl ether was slurried with 10 grams of 5% ruthenium on alumina at 130°C. under ambient pressure of nitrogen gas. A conversion of 85.7% to prop-1-enyl glycidyl ether was observed after the first 18 hours. After 42 hours, a 98.5% conversion was achieved. This product was recovered by filtration and distillation and was analyzed and found to have a cis/trans ratio of 55%/45%.

EXAMPLE 8

To a 500 ml glass reactor equipped with a condenser, mechanical stirrer, thermometer, and nitrogen inlet, 100 g. of polyethylene glycol of average molecular weight 400, 115 g. allyl chloride, 60 g. sodium hydroxide and 100 cc toluene were charged. This mixture was agitated and heated to 50^βC. under nitrogen with vigorous stirring. A mild exotherm raised the temperature of the reaction pot to 65°C. After 2 hours the reaction cooled to 50^βC. , whereupon 5 grams of tetra t-butylammonium bromide in 10 cc of allyl chloride were added to the reactor. This caused the reaction to exotherm up to 65°C. for an additional two hours. After cooling to about room temperature, the reaction mixture was washed with four, 100 cc portions of IN NaOH aqueous solution. The resulting organic layer wa separated and dried with magnesium sulfate and the toluen was removed by rotary evaporation. The remaining product (93 grams) was a clear yellow liquid and the proton NMR indicated the di-allyl ether of polyethylene glycol (MW average 400) .

In a 3-necked reactor 80 g. of the diallyl ether of polyethylene glycol (mol. wt. 400) was dissolved in 10 cc toluene. This mixture was slurried with 5% ruthenium alumina catalyst. After 16 hours proton NMR spectroscopy indicated approximately 20% conversion to the di-prop-1-enyl ether. After 5 days complete conversion w achieved. The product was recovered by filtration to remove the catalyst followed by rotary evaporation of the toluene. The waxy product had a light yellowish color.

EXAMPLE 9

In a 3-liter glass reactor equipped with a condenser, mechanical stirrer, thermometer and nitrogen inlet, 600 g. triethylene glycol, 760 g. allyl chloride, 400 g. sodium hydroxide, and 500 cc of toluene were combined. The reaction mixture was stirred and heated to 55^βC. whereupon a vigorous exothermic reaction began. An ice bath was placed around the reactor and the reaction maintained itself at 70-85°C. for several hours. After t reaction cooled to near room temperature, the contents of the flask were washed with 3 one liter portions of water. The resulting organic layer was separated and dried with magnesium sulfate and the toluene was removed by rotary evaporation. The remaining crude product was distilled a reduced pressure on a 15 plate Oldershaw column (109^βC. a 0.5 mm Hg) to yield 620 g. of product (99.7% purity) diallyl ether of triethylene^" glycol. The product was characterized by proton NMR. Ten grams of diallyl ether of triethylene glycol were vigorously stirred with 0.5 g. of 5% ruthenium on alumina at 120°C. under air. After 16 hours analysis by gas chromatography and proton NMR indicates virtually complete conversion to the correponding di-prop-l-enyl ethers of triethylene glycol CH₃CH=CHO(C₂H₄0)₃CH=CHCH₃. The isomer distribution is as follows: cis, cis - 36.3%; cis, trans - 46.8% and trans, trans - 16.9%.

EXAMPLE 10

In a two liter glass rector equipped with a condenser, thermometer, mechanical stirrer and nitrogen inlet the following reagents were combined : 432 g. of polypropylene glycol of average molecular weight 1025 g/mol, 194 g. allyl chloride, 102 g. sodium hydroxide and 500 cc of toluene. The reaction mixture was vigorously stirred and heated to 55^βC. whereupon a mild exotherm ensued which raised the temperature of reaction pot to 70°C. After one hour the reaction cooled to 55°C. , whereupon 10 g. of tetra-t-butyl ammonium bromide was added to the stirred mixture. The temperature of the reaction rose again to 70°C. and heating was maintained at this temperature for an additional four hours. After cooling, the reaction mixture was washed three times with 500 cc portions of water. The resulting organic layer was separated and dried with magnesium sulfate and the toluene was removed under reduced pressure. The remainig product (485 g.) was a clear yellow liquid which was identified by proton NMR as the diallyl ether of polypropylene glycol (MW 1025) . 350 g. of the diallyl ether of polypropylene glycol (1025) was slurried vigorously under-nitrogen with 10 g. of 5% ruthenium on alumina at 140^βC. After 16 hours proton NMR indicated complete conversion of the allyl ethe groups to prop-l-enyl ether groups. The final product was isolated by filtration to yield a clear yellow product. The proton NMR spectrum indicated the di-prop-l-enyl ether of polypropylene glycol (1025) .

EXAMPLE 11

To a two-liter glass reactor equipped with a condenser, thermometer, mechanical stirrer and nitrogen inlet 500 g. of polyethylene glycol of average molecular weight 1000, 230 g. allyl chloride, 120 g. sodium hydroxide, and 500 cc of toluene were charged. The reaction mixture was stirred and heated to 55°C. whereupon an exotherm ensued which raised the temperature of the system to 75-80°C. After two hours the temperature of the reaction fell to 55°C. , whereupon 5 g. of tetra-trbutyl ammonium bromide was added to raise the temperature to 75-80°C. After two more hours the reactor was cooled to about room temperature. The reaction mixture was washed four times with one liter portions of saturated NaCl solution. The resulting organic layer was separated and dried with magnesium sulfate and the toluene was removed under reduced pressure. The remaining product, 160 g., wa an off white waxy solid of the diallyl ether of polyethylene glycol-1000 as indicated by its proton NMR spectrum.

This product was slurried with 3.2 g. of 5% ruthenium on alumin at 140^βC. under nitrogen. After 16 hours complete conversion to the corresponding cis, trans mixture of di-prop-l-enyl ether of polyethylene glycol-100 was achieved. This material is an off white waxy solid. EXAMPLE 12

To a three liter glass reactor equipped with a mechanical stirrer, condenser, thermometer, and nitrogen inlet, 500 g. of polytetrahydrofuran (average molecular weight 250 g/mol) , 500 cc toluene, 240 g. sodium hydroxide, 459 g. allyl chloride and 10 g. tetrabutyl ammonium bromide were charged. This mixture was vigorously stirred and heated to 50°C. under a nitrogen atmosphere. After 15 minutes at 50°C. a mild exotherm ensued which raised the pot temperature to 70^βC. After several hours the reaction was allowed to cool to 50^βC. at which temperature it remained for an additional three hours. After cooling to room temperature the crude reaction mixture was washed with: 500 cc 0.01 m H₂S0₄ and then again with two 500 cc portions of water. The resulting aqueous and organic layers were separated and the organic layer was dried over magnesium sulfate after which the toluene was stripped off under reduced pressure. The remaining product (438 g.) of diallyl ether of poly(tetrahydrofuran) , MW 250 was a waxy solid.

400 grams of the diallyl ether of poly-(tetrahydrofuran) were vigorously stirred with 10 g. of 5% ruthenium on alumina catalyst at 135-140^βC. under a nitrogen atmosphere. After 18 hours proton n r spectroscopy indicated complete conversion of allyl to prop-1-enyl groups. The final product, isolated after filtration; was a clear oil material, which slowly solidified upon standing for several days. NMR spectroscopy confirmed the structure to be the di-propenyl ether of poly-(tetrahydrofuran) , MW 250. EXAMPLE 13

The diallyl ether of polytetrahydrofuran (average molecular weight of 1000 g/mol) was prepared using the sam procedure as described in Example 12. This product is a clear oily liquid.

400 grams of diallyl ether of said poly-(tetrahydrofuran) was vigorously slurried with 10 g. of 5% ruthenium on alumina at 140°C. under nitrogen. Afte 20 hours, complete conversion of allyl to propenyl groups was achieved. After filtering under pressure, 370 g. of a colorless low melting solid product, i.e. the di-propenyl ether of poly-(tetrahydrofuran) (MW 1000) was obtained.

EXAMPLE 14

To a two liter glass reactor equipped with a mechanical stirrer, thermometer, Dean-Stark trap condenser and nitrogen inlet, was charged 550 g. of Pegol L 31* (a block copolymer of the following formula HO-(EO)₂-(PO)₁₆-(EO)₂-H),

500 cc toluene, and 40 g. sodium hydroxide dissolved in 100 g. water. While stirring, the reactor was heated to 105-110°C. Ninety five cc of water was removed over a 20 hour period after which 78 g. of allyl chloride was slowl dripped over 3 hours into the reaction pot. The mixture was then heated to 105°C. and held at that temperature fo 9 hours, while removing 15 addtional grams of water. The diallyl ether product a yellow oily liquid, was recovered by using a procedure of Example 13.

* Supplied by GAF Corp. 400 grams of said diallyl ether of Pegol L31, i.e. CH₂=CHCH₂0-(EO)₂-(PO)₁₆-(EO)₂-CH₂CH=CH₂, was slurried with 10 g. of 5% ruthenium on alumina and heated to 140^βC. After 40 hours, substantially complete conversion of the allyl groups to propenyl groups was achieved. After filtration, the product

CH₃CH=CH-0-(E0)₂-(PO)₁₆-(E0)₂-0CH=CH-CH₂

was recovered as a yellow oily liquid.

EXAMPLE 15

The diallyl ether of a propylene oxide/ethylene oxide/propylene oxide block copolymer, Pegol 17R2, was prepared using a procedure of Example 14. The resulting product,

CH₂=CH-CH₂0-(PO)₁₂-(EO)_g-(PO) ₁₂-CH₂CH=CH₂,

was a clear oily liquid.

250 grams of the product described above was slurried with 10 g. of 5% ruthenium/alumina catalyst at 140°C. under a nitrogen atmosphere. After 50 hours, proton NMR indicated complete conversion of allyl to propenyl groups. The crude reaction mixture was filtered to yield 235 g. of

CH₃CH=CH₂0(PO)₁₂-(EO)g-(PO)₁₂-CH=CH-CH₃

as a yellow oily liquid. EXAMPLE 16

To a two liter glass reactor equipped with a mechanical stirrer, thermometer, condenser, and nitrogen inlet 300 g. triethylene glycol was added, 416 g. 3-chloro-2-methyl propene, 200 g. sodium hydroxide and 400 cc toluene. This mixture was stirred and heated to 55°C. whereupon a mild exotherm ensured which raised the temperature to 70-75°C. After the exotherm ceased, 5 g. o tetra-t-butyl ammonium bromide was added to the reaction mixture and heating was continued at 60°C. for several additional hours. The reaction was then cooled to about room temperature, filtered, and the toluene removed under reduced pressure. The product was purified by distillatio on a 15 plate Oldershaw column (123°C. at 1.4 mm Hg) . 300 grams of more than 99% pure product was the di-methylallyl ether of triethylene glycol, was recovered.

100 grams of said product was slurried with 2 g. of 5% ruthenium on alumina at 140°C. under nitrogen. Afte 40 hours more than 98% conversion to the methyl prop-l-eny ether was achieved. Pure di 2-methyl prop-l-enyl ether of triethylene glycol was recovered by simple flash distillation at reduced pressure.

EXAMPLE 17

The diallyl ether of propoxylated bisphenol A is prepared according to the procedure of J.A. Crivello and D A. Conlon, in Journal of Polym. Sci. Polymer Che . Ed., Vol. 22, pp 2105-2121 (1984).

100 grams of product prepared above was rapidly slurried with 2 g. of 5% ruthenium on alumina at 140°C. fo 48 hours. Substantially complete conversion to the corresponding di-propenyl ether was achieved. The product was isolated by filtration to yield a clear yellow liquid. EXAMPLE 18

In a glass reactor, 350 g. of the tetra-allyl ether of pentaerythritol and 10 g. of 5% ruthenium on alumina are slurried under nitrogen at 140°C. for 40 hours. A clear yellow product, namely the tetraprop-1-enyl ether of pentaerythritol,

C[CH₂OCH=CHCH₃]₄ ,

is recovered in greater than 80% yield.

EXAMPLE 19

In a glass reactor, 350 g. of the tetra-allyl ether of pentaerythritol and 20 g. of 5% rhodium on alumina are slurried under nitrogen at 140°C. for 96 hours. A clear yellow product, namely the tetraprop-1-enyl ether of pentaerythritol,

C[CH₂OCH=CHCH₃]₄ ,

is recovered by filtering off the rhodium catalyst.

EXAMPLE 20

In a 3-necked reactor 80 g. of the diallyl ether of polyethylene glycol (mol. wt. 400) is dissolved in 100 cc toluene. This mixture is slurried with 5% rhodium on alumina catalyst. After 5 days complete conversion is achieved. The product is recovered by-filtration to remove the catalyst followed rotary evaporation of the toluene. The waxy product had a light yellowish color. EXAMPLE 21

Ten grams of diallyl ether of triethylene glycol is vigorously stirred with 0.5 g. of 5% rhodium on carbon at 120°C. After 96 hours conversion to the correponding di-prop-l-enyl ethers of triethylene glycol, CH₃CH=CHO(C₂H₄0)₃CH=CHCH₃, is achieved.

It will be understood that any alk-2-enyl ether, particularly those specifically designated in the foregoin disclosure can be substituted in the above examples and that any of the above described catalyst supports can be substituted for alumina to effect the conversion of alk-2-enyl ethers to the corresponding alk-l-enyl ethers o this invention.

Claims

WHAT IS CLAIMED IS:

1. A composition comprising an alk-2-enyl ether and between about 0.1 and about 20 wt. % of supported rare metal catalyst of atomic number 44 or 45 where the amount of metal with respect to support is between about 0.05 and about 10 wt. %.

2. The composition of claim 1 wherein said metal is ruthenium.

3. The composition of claim 1 or 2 wherein said alk-2-enyl ether has the formula

wherein R' is hydrogen or a radical having from 1 to 20 carbon atoms and is selected from the group of aryl, alkaryl, aralkyl, alkyl and alkoxy or R' , together with the oxygen atom of the -CH=CY-CH₂0- moiety, forms a 4 to 6 membered heterocyclic ring; Y is hydrogen or lower alkyl; n has a value of from 0 to 50; Z is an aliphatic radical having from 1 to 10 carbon atoms and is selected from the group of alkylene, alkyleneoxy, alkenylene, alkenyleneoxy, alkynylene, alkynyleneoxy, alkyleneoxy, carboxylate and aminocarboxylate; x has a value consistent with the number of free valences in R and R is hydrogen or a mono- or poly¬ valent radical having from 1 to 20 carbon atoms or a polymer thereof and is selected from the group of aliphatic radicals of the group alkylene, alkenylene, alkynylene, alkylarylene, aromatic radicals of the group phenylene, tolylene or xylylene, which radicals are optionally substituted with halo, lower alkyl, lower alkylene, hydroxyalkyl, alkenyloxy, alkenyl, alkoxy, alkylcarbonyl o alkenylcarbonyl; a divalent 3 to 6 membered heterocyclic radical having S, O or N as the hetero atom and the radica

wherein v has a value of from 1 to 50; A is halo, lower alkyl, lower alkoxy or hydroxy; m has a value of from 0 to 2; p has a value of from 0 to 1 and R" is lower alkylene, sulfone, sulfur or oxygen.

4. The composition of claim 1, 2 or 3 wherein said alk-2-enyl ether is octyl prop-2-enyl ether.

5. The composition of claim 1, 2 or 3 wherein said alk-2-enyl ether is allyl glycidyl ether.

6. The composition of claim 1, 2 or 3 wherein said alk-2-enyl ether is the allyl ether of the monoethyl ether of triethylene glycol.

7. The composition of claim 1, 2 or 3 wherein said alk-2-enyl ether is diallyl ether.

8. The composition of claim 1, 2 or 3 wherein said alk-2-enyl ether is a polyallyloxy alkyl alkane.

9. The composition of claim 1, 2 or 3 wherein said alk-2-enyl ether is allyloxybenzyl polymer.

10. The composition of claim 1, 2 or 3 wherein said alk-2-enyl ether is the diallyl ether of di(alkoxylated phenyl) alkane having the formula

CH₂=CHCH₂0[CH(Y)CH₂0]_sO-C₈H₄-R-C₆H₄0 [CH(Y)CH₂0]_SCH₂CH=CH₂

where Y is hydrogen or methyl and ε has a value of from 1 to 10.

11. The composition of claim 1, 2 or 3 wherein said alk-2-enyl ether is di(allyloxyalkyl) benzene dicarboxylate.

12. The composition of claim 1, 2 or 3 wherein said alk-2-enyl ether is a polyallyl ether of a poly(alkoxyamido carbonate) alkane having the formula

(CH₂=CHCH₂0R₁00CNH)_nR

where R_χ is alkylene or alkyleneoxy; R is a polyvalent alkyl, aryl, alkaryl or aralkyl radical and n is equal to the number of free valences in R.

13. The composition of claim 1 wherein the amoun of rare metal with respect to support is between about 0.1 and about 5 wt. % and wherein the composition comprises between about 0.5 and about 5 wt. % of said supported rare metal.

14. ^• The composition of claim 13 wherein said rar metal is ruthenium.

15. The composition of claim 1 wherein said support is selected from the group of silica, alumina, silica-alumina, magnesia and carbon.

16. The composition of claim 1 wherein said composition is a slurry.

17. The composition of claim 1 wherein said ally ether is a viscous liquid and the composition additionally contains up to 90 wt. % of an inert solvent.

18. The composition of claim 17 wherein said inert solvent is selected from the group of toluene, xylene, dimethoxy ethane and ethoxyethyl ether.

19. The composition of claim 3 wherein R¹ and Y are hydrogen, n has a value of from 0 to 10 and R is alkylene, alkoxylated alkylene, polyalkylene oxide, or 2,2-diphenyloxy propane.

20. The process which comprises contacting a supported rare metal catalyst and an alk-2-enyl ether under a blanket of inert gas at a temperature of from about 60° to about 200°C. under a pressure of from about 14 to about 500 psi to produce the corresponding alk-l-enyl ether isomer.

21. The process of claim 20 wherein said rare metal is ruthenium.

22. The process of claim 21 wherein the alk-2-enyl ether is contacted with the supported ruthenium catalyst for a period of from about 2 hours to about 6 days.

23. The process of claim 22 wherein said alk-2-enyl ether is contacted with said supported ruthenium catalyst at a temperature of from about 100° to about 160°C. under from about 14 to about 50 psi for a period of from about 4 to about 24 hours.

24. The process of claim 20, 21, 22 or 23 wherein said alk-2-enyl ether is diluted up to 90% with an inert liquid having a reflux temperature below that of the alk-l-enyl ether isomeric product before contact with said supported rare metal catalyst.

25. The process of claim 21, 22 or 23 wherein between about 0.1 and about 20 wt. % of the supported ruthenium catalyst in which the concentration of ruthenium to support is between about 0.05 and about 10 wt. %, is contacted with the allyl ether.

26. The process of claim 20-25 wherein the isomerization reaction is carried out using a fixed bed of said supported rare metal catalyst.

27. The process of claim 18 wherein the isomerization reaction is effected with a liquid slurry of alk-2-enyl ether and catalyst.

28. The process of claim 20 wherein said alk-2-enyl ether has the formula

wherein R¹ is hydrogen or a radical having from 1 to 20 carbon atoms and is selected from the group of aryl, alkaryl, aralkyl, alkyl and alkoxy or R¹, together with th oxygen atom of the -CH=CY-CH₂0- moiety, forms a 4 to 6 membered heterocyclic ring; Y is hydrogen or lower alkyl; has a value of from 0 to 50; Z is an aliphatic radical having from 1 to 10 carbon atoms and is selected from the group of alkylene, alkyleneoxy alkenylene, alkenyleneoxy alkynylene, alkynyleneoxy, alkyleneoxy, carboxylate and aminoσarboxylate; x has a value consistent with the number of free valences in-R, and R is hydrogen or a mono- or poly- valent radical having from 1 to 20 carbon atoms or a polymer thereof and is selected from the group of aliphatic radicals of the group alkylene, alkenylene,^' alkynylene, alkylarylene, aromatic radicals of the group phenylene, tolylene or xylylene, which radicals are optionally substituted with halo, lower alkyl, lower alkylene, hydroxyalkyl, alkenyloxy, alkenyl, alkoxy, alkylcarbonyl or alkenylcarbonyl; a divalent 3 to 6 membered heterocyclic radical having S, 0 or N as the hetero atom and the radical

29. The process of claim 28 wherein R' and Y of said alk-2-enyl ether is hydrogen or lower alkyl, n has a value of from 0 to 10 and R is alkylene, alkoxylated alkylene, polyalkylene oxide or 2,2-diphenyloxy propane.

30. The process of claim 29 wherein said alk-2-enyl ether is octyl allyl ether.

31. The process of claim 29 wherein said alk-2-enyl ether is an allyl glycidyl ether.

32. The process of claim 29 wherein said alk-2-enyl ether has the formula

0 CH₂=CHCH₂OCH₂-CH-CH₂

33. The process of claim 29 wherein said alk-2-enyl ether has the formula

where Y is hydrogen or methyl.

34. The alk-l-enyl isomeric product of claim 20 in greater than 90% purity.

35. The alkoxylated prop-l-enyl ether having t formula

R'CH_jCH-^CR¹ • '0(B)_wCH=CR' 'CH₂R'

wherein R' is hydrogen or a radical having from 1 to 20 carbon atoms and is selected from the group of aryl, alkaryl, aralkyl, alkyl and alkoxy; R' * ^• is hydrogen or lower alky; B is alkyleneoxy having from 2 to 4 carbon atoms and w has a value of from 3 to 10.