DE1593263B2 - METHOD OF CATALYTIC CONVERSION OF AN ALKENYLCYCLOHEXENE AND 1,2-BIS- (3'-CYCLOHEXENYL- (1 ') -ETHYLENE AS SUCH - Google Patents

Description

R 'R'

According to the prior art, there are no commercial processes for the synthesis of bis- (cyclohexenyl) -substituted ones Olefins are known in which the double bonds are in a non-conjugated relationship be brought to each other.

It is known, l, 2-bis- (l'-hydroxycyclohexyl) -äthylen to conduct at reduced pressure and a temperature in the range 325-350 ⁰ C over aluminum oxide, which is to l, 2-bis (l ' -cyclohexenyl- (l ')) - ethylene is dehydrated. However, the double bonds in this compound are in the conjugated position. It is a decisive advantage to be able to prepare bis (cyclohexenyl) - substituted olefins in which the double bonds are in the non-conjugated position, because with compounds which have such a structure, larger-scale reactions can be carried out in which the double bonds are independent react from each other.

The invention therefore relates to a process for the catalytic conversion of an alkenylcyclohexene, which is characterized in that for the preparation of a non-conjugated bis (cyclohexenyl) alkene a non-conjugated alkenylcyclohexene having no more than 20 carbon atoms in the molecule in the presence a catalyst is implemented, which is an oxide of molybdenum or tungsten on an oxide of Contains silicon or aluminum as a carrier. It has been found that it is possible to adjust the reaction conditions to be controlled so that one avoids alkylation, polymerization and dehydrogenation reactions. The inventive method is in

where only one R 'in the molecule

35 ' R "\ R" R "

-C = C-R "

VR " L

and in which the remaining R 'radicals are selected from the group consisting of hydrogen and alkyl, aryl and cycloalkyl radicals and combinations thereof (e.g. aralkyl and alkaryl) containing 1 to 10 carbon atoms, R "from the group hydrogen, alkyl, aryl and cycloalkyl radicals and combinations thereof (such as z. B. aralkyl and alkaryl) containing 1 to 10 carbon atoms are selected, with the R "groups may be identical or different, »is an integer from 0 to 4 inclusive and the Total number of carbon atoms in one of the alkenyl-substituted cyclohexenes mentioned 20 not exceeds. Preferred alkenyl-substituted cyclohexenes are those in which the alkenyl radical does not have any branching on the carbon atom involved in the double bonds.

Some specific examples of alkenyl-substituted cyclohexenes made by the process of the invention can be converted into bis (cyclohexenyl) - substituted olefins are 4-vinylcyclohexene, 2,3 - dimethyl - 4 - vinylcyclohexene, 2 - phenyl - 6 - (3'-cyclohexenyl - (1 ')) - hexene - (I), 3 - cyclohexyl - 4 - vinylcyclohexene, 3-benzyl-4- (l'-methylvinyl) cyclohexene,

4 - (Γ - Cyclohexenyl - (Γ)) - 3,3 - dimethylbutene - (1), 1 - methyl -4 - (1 '- methylvinyl) - cyclohexene, 3 - methy I-

5 - (propenyl) cyclohexene. 3 - methyl - 4 - (propenyl) cyclohexene. 3,4-dimethyl-5-vinylcyclohexene, 3,5-dimethyl-4-vinylcyclohexene and mixtures thereof.

The bis (cyclohexenyl) substituted olefins prepared according to the invention can be represented by the formula

R R

RRRR

are represented, in which R is at least one radical selected from the group consisting of hydrogen, alkyl, aryl, cycloalkyl, Aralkyl, alkaryl containing 1 to 10 carbon atoms, and wherein the total number of carbon atoms Does not exceed 20 is selected.

Some specific examples are l, 2-bis- (3'-cyclohexenyl- (T)) - ethylene, 1,2 bis ~ (2 ', 3'-dimethyl-3'-cyclohexenyl- (l')) ethylene, 5,6-Diphenyl-l, 10-bis (3'-cyclohexenyl - (1 ')) - decene - (5), 1,2 - bis - (cyclohexyl - (3') - cyclohexenyl - (1 ')) - ethylene, 2,3 - bis - (2' - benzyl -3'-cyclohexeny 1 - (1 ')) - butene - (2), 2,5 - dimethyl - 1,6-bis -(1' - cyclohexenyl - (1 ')) - hexene - (3), 2,3 - bis - (4 - methyl-3'-cyclohexenyl- (1')) - butene (2), 1,2-bis- (3'-methyl-3'-cyclohexenyl- (1 ')) -ethylene, 1,2-bis- (2'-methyl-3'-cyclohexenyl- (l')) - ethene, 1,2-bis (2 ', 3'-dimethyl-4'-cyclohexenyl- (l')) -ethylene, 1,2-bis- (2 ', 6'-dimethyl-3'-cyclohexenyl- (l ')) - ethylene, 1 -Methyl- 1- (4'-methyl-3'-cyciohexenyl- (l ')) - 2- (3'-cyclohexenyl- (l')) - ethylene.

The catalysts used in the process according to the invention are conventional ones on a carrier applied molybdenum or tungsten catalysts; Suitable carriers are silicon dioxide, aluminum oxide and aluminum oxide, which contains masses, the smaller amounts of other substances involved in the reaction are compatible, contain such. B. small amounts of silicon dioxide, titanium oxide, magnesium oxide, cobalt oxide. Molybdenum or tungsten can be added to the carrier in the form of a molybdenum or tungsten compound be admitted; z. B. can molybdenum hexacarbonyl, tungsten hexacarbonyl, ammonium tungstate, Molybdenum oxide, tungsten oxide or molybdenum and tungsten compounds which can be converted into the oxide by calcining, be used. The addition of the molybdenum or tungsten compound to the carrier can be carried out according to conventional methods Process such as B. dry mixing, co-precipitating or saturating, take place. The saturation will preferred here. The amount of molybdenum present in the resulting composite catalyst or tungsten is generally from 0.1 to 30 percent by weight, preferably 3 to 15 percent by weight (calculated as oxide) of the total catalyst mass. Catalysts are preferred here, those by combining a molybdenum compound with aluminum oxide along with a small amount an alkali metal compound.

The preparation and activation of the composite catalyst are common and can be accomplished in a number of ways. For example, when using molybdenum hexacarbonyl as the molybdenum-providing compound, it is preferred to use the carrier, e.g. B. aluminum oxide, to a temperature above 260 ° C, preferably to a temperature of about 400 to about 800 ⁰ C in the presence of oxygen, generally to be heated for 5 minutes. The addition of molybdenum hexacarbonyl to the carrier can be accomplished by contacting that carrier with an RRRR

Hydrocarbon solution of the molybdenum compound take place, which is then heated under vacuum. In those cases in which other molybdenum or tungsten compounds are used as the catalyst, the saturation of the carriers with a dispersion of the molybdenum or tungsten compound is preferably carried out prior to the heating described above. Whichever molybdenum or tungsten compound is used, the use of supports ^{having a surface area of about 100 to 300 m 2} / g is preferred. It is also preferred to use non-acidic carriers, with alumina being the most preferred carrier in order to minimize double bond isomerization which leads to a greater number of olefin products. Sometimes it is advantageous to add small amounts of alkali or alkaline earth metal compounds to the catalyst prior to the heating step. The regeneration of the catalyst, if applicable, is completed by conventional means. For example, a used catalyst made from ammonium molybdate and aluminum oxide is reheated in an oxygen-containing gas stream for a sufficient time to restore its activity.

The process can be carried out in the presence or absence of an inert diluent The amount of diluent is generally about 0 to 90 percent by volume of the reaction mixture. Suitable diluents are saturated hydrocarbons, such as z. B. alkanes and cycloalkanes. Some examples are cyclohexane, cycloheptane, hexane, octane, decahydronaphthalene and mixtures thereof.

It is within the scope of the present invention that the process can be carried out in batches or as continuous process can be carried out in either the liquid or vapor phase. That Working in the liquid phase is preferred here. In the batch process, the catalyst works generally from about 0.5 to about 25 percent by weight of the reaction mixture. At work in a continuous process, the catalyst can be used as a fixed bed over which the alkenyl substituted cyclohexenes at an appropriate rate to achieve the desired Reactions are conducted under the chosen reaction conditions.

A convenient batch method of carrying out the reaction is to use a Catalyst bed fixed in a fractionating column above the boiler. As the end products, bis- (cyclohexenyl) -substituted olefins, in most cases above the introduced alkenyl-substituted Cyclohexene boiling, the feed can be brought into the kettle and passed through the catalyst bed to be vaporized at the top. The product will then be in

reflux in the kettle, and the by-product olefins can generally overhead go off. This process represents a combined conversion and separation process.

After the reaction time, the bis- (cyclohexenyl) -substituted olefin is separated off and not from the converted alkenyl-substituted cyclohexenes and the by-products by one of the usual methods, such as B. fractionation, liquid extraction or adsorption, isolated. If the feed z. B. 4-vinylcyclohexene, the by-product can be ethylene removed as a gas and the product l, 2-bis (3'-cyclohexenyl- (l ')) - ethylene can from the feed and the other olefinic by-products are separated by fractionation.

example 1

200 g of a granular cobalt molybdate catalyst on alumina containing 3.42 percent by weight CoO, 11.0 percent by weight MoO ₃ and 85.6 percent by weight Al ₂ O ₃ were treated with 185 ml of an aqueous solution containing 2.2 g of KOH. After 30 minutes the catalyst granules were removed, dried under vacuum and ^{heated to 500 °} C. for 5 hours.

In a 500 ml distillation pot, 170 ml (142 g) of neat (Phillips) 4-vinylcyclohexene was placed and blanketed with a nitrogen atmosphere. The pot was then on. a distillation column which was filled with nitrogen and through which a constant stream of nitrogen flowed attached. The column had a diameter of 18 mm and was 13 cm high filled with stainless steel packing. The top of the column was removed and 34.6 g of the above-described catalyst was charged to the top of the column under a nitrogen atmosphere, after which the top was replaced. Das4-Vinylcyclohcxen was then boiled for 2 hours under reflux, which passed through the catalyst bed, during which time a constant Äthylenentwicklung was found and the kettle temperature rose from 128 to 190 ⁰ C. After 2 hours the heating was stopped and the reaction mixture was allowed to cool. The material absorbed on the catalyst was removed by refluxing the column and the catalyst bed with n-pentane and then evaporating the pentane. The combined products were then fractionated under reduced pressure, with the unchanged vinylcyclohexene being driven over into a dry ice trap.

This fractionation resulted in the following:

fraction

Vol.
(ml)

Weight
(G)

Temp.
( ⁰ C)

pressure

1 «3 2.4 79 0.3 mm Ed 2 80 73.6 79-80 0.3 mm Ed Residue

The above catalytic reaction was repeated a few times and the product fractions obtained from each experiment were combined. Nuclear Magnetic Resonance (NMR) analysis of the sample of the combined product indicated that the material was a mixture containing 1,2-bis (cyclohexyl (V)) ethylene (BCE). Infrared analysis of the material showed that the unsaturation, unlike observed in the cyclohexene rings, was essentially transconfiguration.

A 500 g sample of the mixture of 1,2-bis (cyclohexcnyl-l) -äthylcn (BCE) prepared above was carefully fractionated at 1 to 2 mm absolute pressure, whereby a fraction with 99.6% purity (determined

ίο obtained by gas - liquid chromatography) became.

GFC analysis of the fractionated material *)

Purity in

GcwiclusproV.cnl

BCE

First parliamentary group 60

Second fraction 98.4

Third parliamentary group 99.6

*) A 457 cm long Apic / .onkapillarc was used, which was suitable for 60 to 220 C.

An elemental analysis of the third fraction (99.6% purity) gave the following results:

Elemental analysis C ₁₄ H ₂₀ :

Calculated ... C 89.3, H 10.7;

found .... C 89.3, H 10.8;

C 89.2, H 10.8.

An ultraviolet ray spectrum of the material indicated that it was a non-conjugate olefin.

This third fraction had the following physical Characteristics:

Density d- ''' 0.924

tvg 1.5103

Boiling point at 1 mm 90 ⁰ C

A 1.0 ml sample (0.9242 g) of the material of 98.4% purity was hydrogenated in glacial acetic acid using a prereduced PtO ₂ catalyst at 755 mm of mercury absolute hydrogen pressure, at 25 ° C and using hydrogen saturated with water vapor. Under these conditions the sample absorbed 381.9 ml of hydrogen. This corresponds to 3.05 double bonds per molecule.

Example II

In this example, 4-vinylcyclohexene was converted to 1,2-bis (3'-cyclohexenyl- (l ')) ethylene using a continuous conversion process. 30.5 g (57.5 ml) of a commercially available molybdenum oxide-aluminum oxide catalyst were placed in a vertical glass reaction vessel with a diameter of 22 mm and a length of 30 cm. The catalyst contained 13.0 percent by weight of molybdenum oxide and had a surface area of 325 m ² lg, a pore volume of 0.52 cm ³ / g and a pore diameter of 64 Å. The catalyst was treated with an approximately 2 weight percent potassium hydroxide solution and activated in substantially the same manner as the Example I catalyst prior to introduction into the reaction vessel. The glass vessel was provided with an insulating jacket in which a refluxing heat exchange liquid was placed in order to maintain the desired temperature.

The 4-vinylcyclohexene was left at 120-124 ° C

and atmospheric pressure through the reaction vessel, with an hourly throughput rate of the liquid of 1.4 Vol./Vol./Std."fließen. (The vinylcyclohexene filling had been pretreated by rapid distillation over _FeSO4. · 1 H ₂ O to the peroxides before contact with During the course of the test, the ethylene byproduct was allowed to escape through an opening at the top of the reaction vessel, and the product, other byproducts and unconverted 4-vinylcyclohexene collected at the bottom of the reaction vessel.

A sample of the downflow from this reaction vessel was obtained after 150 minutes of treatment and analyzed by gas-liquid chromatography. A reaction was carried out found by 46.4%. The yield of l ^ -Bis-ß'-cyclohexcnyl-O '^ - ethylene found at the end was 80.9 mole percent. Also about 10.1 mole percent of other isomers of this product as well as about »20 7.9 mole percent heavy olefinic products were obtained. Also about 0.9 mole percent of isomers of 4-vinylcyclohexene were found among the products. (Ethylene did not become one of the by-products The by-products, which were isomers of 1,2-bis- (3'-cyclohexenyl- (l ')) - ethylene, included both olefin isomers of this material (including non-conjugated ones) and some structural isomers that identified as 1 - cyclohexenyl - 3 - cyclopentenylpropene.

The substituted ethylene prepared according to the invention are useful as chemical intermediates. One such application is the isomerization of 1,2-bis (3'-cyclohexenyl- (l ')) ethylene (= BCÄ) to 1 - phenyl - 2 - cycloxylethane, this compound with the formation of dibenzyl below becoming dehydrated. Derivatives of these products are useful as insecticides and fungicides.

Another useful derivative of BCÄ is stilbene.

Yet another derivative of BCE can be obtained by halogenation. These halogenated BCÄ derivatives are used as flame retardants for polyolefins. It was found that polypropylene, in the 1,2-bis (3,4-dibromocyclohexyl) -1,2-dibromoethane was incorporated, no longer burned.

The superior property of the derivative is evident from the fact that it is a very low concentration sufficient to make polypropylene non-flammable. Lots of flame retardant compounds need can be used in much higher concentrations to give the same effect.

The BCÄ can also be used with organic acids such as B. formic acid, acetic acid or propionic acid, be esterified. The ester products are useful as plasticizers.

Another useful derivative of BCE is formed upon treatment with maleic anhydride obtained new succinic anhydride derivatives. The adducts produced in the reaction and Copolymers can be used as hardeners for epoxy resins and as components in alkyd resins will.

When BCA is treated with hydrogen sulfide or a mercaptan, sulfide or mercaptan derivatives become Manufactured as intermediates in the manufacture of pesticides, insecticides and conjugated as a polymerization modifier in emulsion polymerization The synthetic rubbers can be used.

509587/456

Claims (5)

Patent claims: Process for the catalytic conversion of an alkenylcyclohexene, characterized in that that for the production of a non-conjugated bis (cyclohexenyl) alkene a non-conjugated Alkenylcyclohexene with not more than 20 carbon atoms in the molecule in the presence a catalyst is implemented, which is an oxide of molybdenum or tungsten on a Contains oxide of silicon or aluminum as a carrier. 2. The method according to claim 1, characterized in that the reaction is only up to one Conversion of less than 50% of the alkenylcyclohexene used is carried out. 3. The method according to claim 1 and 2, characterized in that 4-vinylcyclohexene for * production of l, 2-bis- (3'-cyclohexenyl- (l ')) - ethene is used. 4. The method according to claim 3, characterized in that the reaction is carried out at 25 to 300 ⁰ C in the presence of a catalyst which contains cobalt molybdate or molybdenum oxide on an aluminum oxide and which has been treated with potassium hydroxide. 5. 1,2-bis- (3'-cyclohexenyl- (l ')) - ethylene with a density at 25 ° C. of 0.924 g / cm ³ , a refractive index (nf) of 1.5103 and a boiling point at 1 mm Hg of 90 ⁰ C. generally by bringing one or more together Alkenyl-substituted cycloalkenes with a molybdenum or tungsten catalyst applied to a support at a temperature from 25 to 300 ° C, preferably from 75 to 200 "C, for a period of time from about 0.5 seconds to 24 hours or longer depending on the contacting method and depends on the desired degree of conversion, carried out at pressures in the range from 1 to 100 atm. It ίο it is preferred to have a low overall conversion e.g. B. below 50%, and more preferably below 25%, to be used for further conversion of the products to keep less desirable substances to a minimum. The invention also relates to the 1,2-bis (3'-cyclohexyl- (l ')) ethylene mentioned in the preceding claim 5 as such, which has the characteristics given in claim 5. The alkenyl-substituted cyclohexenes leading to bis- (cyclohexenyl) -substituted Olefins are converted to have the Fokendc formula