US3219714A - Production of 1,5-cyclo-octadiene from butadiene - Google Patents

Production of 1,5-cyclo-octadiene from butadiene Download PDF

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US3219714A
US3219714A US121362A US12136261A US3219714A US 3219714 A US3219714 A US 3219714A US 121362 A US121362 A US 121362A US 12136261 A US12136261 A US 12136261A US 3219714 A US3219714 A US 3219714A
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nickel
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octadiene
phosphite
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Kutepow Nikolaus Von
Seibt Hubertus
Meier Fritz
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BASF SE
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
    • C07F15/04—Nickel compounds
    • C07F15/045—Nickel compounds without a metal-carbon linkage
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
    • B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
    • B01J31/1845—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing phosphorus
    • B01J31/185—Phosphites ((RO)3P), their isomeric phosphonates (R(RO)2P=O) and RO-substitution derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
    • C07C2/02—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons
    • C07C2/42—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons homo- or co-oligomerisation with ring formation, not being a Diels-Alder conversion
    • C07C2/44—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons homo- or co-oligomerisation with ring formation, not being a Diels-Alder conversion of conjugated dienes only
    • C07C2/46—Catalytic processes
    • C07C2/465—Catalytic processes with hydrides or organic compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
    • C07F15/04—Nickel compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
    • B01J2231/32—Addition reactions to C=C or C-C triple bonds
    • B01J2231/324—Cyclisations via conversion of C-C multiple to single or less multiple bonds, e.g. cycloadditions
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
    • B01J2531/84—Metals of the iron group
    • B01J2531/847—Nickel
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2531/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • C07C2531/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2531/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • C07C2531/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • C07C2531/22—Organic complexes
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/18—Systems containing only non-condensed rings with a ring being at least seven-membered

Definitions

  • butadiene It is known to dimerize 1,3-butadiene, hereinafter referred to briefly as butadiene, by thermal non-catalytic methods to 1,5-cyclo-octadiene and 4-vinylcyclohexene- (1). Only a small proportion of 1,5-cyclo-octadiene is thus obtained. An increase in this proportion is achieved by the use of nickel-containing catalysts at temperatures between 90 and 150 C. and at increased pressure in the presence or absence of solvents. Thus, nickel cyanide and complex nickel compounds have been used as catalysts, for example nickel carbonyls in which at least one carbonyl group has been replaced by an organic phosphite.
  • nickel complex compounds which contain no carbon monoxide and in which the nickel is O-valent.
  • Complexes of this kind are nickel(0) complexes with e s-unsaturated aldehydes and with one-unsaturated nitriles.
  • Examples of complexes of this kind are: nickel(0)-bis-acrolein, nickel(0)- bis acrylonitrile, nickel(0)-biscinnamonitrile and nickel O) -bis-fumaronitrile.
  • nickel complexes are combined by means of the 1r-electrons contained in the olefinic double linkages.
  • the readily accessible nickel-bis-acrylonitrile is preferred.
  • esters of phosphorous acid there are used those of aliphatic alcohols, especially those with branched chains, for example a-lkanols with 1 to 12 carbon atoms, but mainly of aromatic hydr-oxy compounds, such as phenols and naphthols.
  • the phenols and naphthols may be substituted by alkyl radicals, aryl radicals, halogen atoms or alkoxy groups, for example by one to three alkyl radicals with 1 to 12 carbon atoms or by phenyl radicals. It is especially advantageous to use phenyl esters of phosphorous acid in which substituents are present in o-position to the phenolic hydroxy group.
  • phosphites which may be used are: trimethyl phosphite, triethyl phosphite, tri-isopropyl phos-, phite, tri-iso-butyl phosphite, tri-(Z-ethylhexyl) phosphite, tridodecyl phosphite, triphenyl phosphite, tri-o-cresyl phosphi-te, -tri-m-cresyl phosphite, tri-p-cresyl phosphite, tri-(2, 4-dimethylphenyl) phosphite, tri-o-isopropylphenyl phosphite, tri-(2,6di-methylphenyl) phosphite, tri-p-iso-butylpheny-l phosphite, tri-p-isooctylphenyl pho
  • reaction between the organic nickel complex free from carbon monoxide and the phosphite may be reproduced for example with nickel-bis-acrylonitrile and triphenyl phosphite as follows:
  • the reaction of these components to form the catalysts to be used according to this invention is effected by mixing the organic nickel(0) complex free from carbon monoxide with the phosphite in about the mol ratio 1:05 to 1:5, preferably in the ratio 1:3 to 1:5, with substantial exclusion of oxygen in a solvent or diluent inert under the reaction conditions at room temperature or at an elevated temperature, i.e., at a temperature between about 20 and about C.
  • substantial exclusion of oxygen we mean that the oxygen content in the gas space above the liquid reaction mixture in the reaction vessel should not exceed about 3 vol. percent. If larger amounts of oxygen are present, substantial amounts of nickel(0) complex will be decomposed.
  • this reaction is carried out at normal pressure but it may also be carried out under increased or reduced pressure.
  • Suitable solvents are aliphatic, cycloaliphatic and aromatic hydrocarbons, ethers and nitriles of lower fatty acids, especially those whose boiling point at the pressure chosen lies in the temperature range of 20 to 120 C. This means that usually solvents boiling between 20 and 120 C. at normal pressure are used, for example hexane, the various octanes, gasoline fractions of this boiling range, cyclohexane, benzene, toluene, but solvents of lower boiling point may be used when the reaction is carried out under pressure, or of higher boiling point when the reaction is carried out, often with advantage, under reduced pressure.
  • Xylene, tetrahyd'ronaphthalene, decahydronaphthalene and liquid butane or propane may therefore also be used.
  • nitriles for example diethyl ether, di-isopropyl ether, diisobutyl ether, dioxane or tetrahydrofurane.
  • nitriles the most suitable are those with two to five carbon atoms, for example acetonitrile and pro-pionitrile.
  • the ratio of the reactants (nickel complex and phosphite) to the solvent or diluent may vary within wide limits; it is possible to use saturated solutions in which the organic nickel complex is suspended, but very dilute solutions may also be used although it is not convenient to work in a greater dilution than 1 part of nickel complex to 10 parts of solvent.
  • the progress of the reaction can readily be recognized by the change in color of the reaction mixture.
  • the nickel complex solution or suspension is as a rule red in color. It changes its color toward yellow or becomes colorless, and at the same time the phosphite-containing nickel complex may be precipitated in solid form. In general the reaction is ended after 1 to 2 hours.
  • the complex is precipitated in insoluble form, it is filtered off by suction, washed with an organic solvent and dried. If it remains in solution, this solution mayeit her be used directly for the dimerization or the solvent can be distilled off and the residue used for the dimerization. In some cases it may be convenient to precipitate the complex formed by adding lower alcohols, for example methanol, ethanol or propanol. All operations are preferably carried out while excluding oxygen. In many cases definite new compounds are obtained, for example of the composition wherein R represents a member selected from the group consisting of alkyl, aryl, alkylaryl and halogenaryl,
  • Z represents a member of the group consisting of 3- ethylenically unsaturated aldehydes and nitriles
  • x stands for an integer of from 2 to 3
  • y stands for an integer of from 1 to 2
  • those phosphites and the above-mentioned a,fi-ethylenically unsaturated compounds are used which above were called especially advantageous.
  • tris- (tri-o-chlorphenyl-phosphite) -nickel and bis- (tri-4 iso-octylphenyl-phosphite -nickel are obtained in this way.
  • the phosphite-containing nickel(0) complexes are yellowish white crystalline compounds.
  • Dimerization of butadiene with the catalysts of the kind described above is effected under the conditions known for this reaction.
  • the catalyst is used in a concentration of about 0.5 to about 5%, preferably 2 to 4% by weight with reference to butadiene. In some cases, however, lower concentrations, for example 0.1% by weight, are sufficient.
  • liquid butadiene also acts as a solvent.
  • saturated and unsaturated aliphatic, cycloaliphatic or aromatic hydrocarbons especially those with a boiling range between and 250 C., such as n-hexane, noctane, gasoline fractions, benzene, toluene, xylenes, p-cymene, cyclohexane, cyclo-octane, cyclo-octadiene alone or in admixture with other solvents, tetrahydronaphthalene, decahydronaphthalene, dicyclopentadiene, and also liquid carboxylic acid amides, such as dimethylformamide, N,N-di-methylacetamide, N-butylpyrrolidone, cyclic ethers, such as dioxane or tetrahydro
  • a polymerization inhibitor to prevent polymerization of the butadiene.
  • Such inhibitors are known; examples are mononuclear or polynuclear monophenols or polyphenols, such as phenol, pyrocatechol, p-tertiary-butylpyrocatechol, resorcinol, 2,4-dimethyl-6-tertiary butyl phenol, hydroquinone, quinones, phloroglucine, pyrogallol and also amines, espe cially N,N'-di-isopropyl p-phenylene-diamine and phe nothiazine. These inhibitors are used in amounts of 0.01 to 3% by weight with reference to the diolefine.
  • Dimerization may be carried out within a wide temperature range above at least 50 C., for example in the range of 50 to 250 C. It is preferred to work between about and 150 C.
  • Dimerization is in general carried out at the pressure determined by the vapor pressure of butadiene, of any solvent used and of the cyclo-octadiene formed, for example in the range of 3 to 20 atmospheres. It is also possible to work at higher pressures by forcing in inert gases, such as nitrogen, rare gases, saturated hydrocarbons, gaseous hydrocarbons containing a single olefinic unsaturation, or carbon dioxide. In principle, however, the process may be carried out at normal pressure, for example by blowing butadiene in gaseous form into a solution of the catalyst in any of the said solvents.
  • inert gases such as nitrogen, rare gases, saturated hydrocarbons, gaseous hydrocarbons containing a single olefinic unsaturation, or carbon dioxide.
  • the butadiene may be used pure or in admixture with other saturated or unsaturated hydrocarbons, for example as obtained in the cracking of higher hydrocarbons.
  • the process may be carried out batchwise, semiconti-nw ou-sly or fully continuously.
  • the catalyst may for exam ple be placed, preferably while excluding oxygen, in a diluent or solvent in an autoclave and liquid butadiene added.
  • the relative proportions of catalyst and butadiene may be varied within wide limits. For example 0.5 to 5 preferably 2 to 4%, by weight of catalyst with reference to butadiene may be used.
  • the autoclave is then heated to the reaction temperature, for example to to 120 C., a pressure of 3 to 20 atmospheres gage being set up depending on the diluent used.
  • the reaction period up to practically complete conversion is in general about 12 to 48 hours.
  • the reaction may be discontinued after only 1 to 2 hours because the bulk, i.e., about 80 to of the maximum amount is converted Within this time.
  • the conversion naturally depends on the activity of the, catalyst and with some catalysts a satisfactory degree of conversion can be reached after only 10 to, 2 minutes.
  • reaction product which is liquid at room temperature and which, if desired after filtration, is fractionally distilled.
  • the main fraction passing over is 1,5-cyclo-octadiene.
  • Small amounts of 4-vinyl-cyclohexene-(l) are obtained as byproduct and small amounts of higher polymers as distillation residue.
  • the process may also be carried out continuously, for example by the so-called trickling method or by introducing the gaseous reactants into the liquid phase.
  • Butadiene may for example be injected into a catalyst solution kept at the reaction temperature and the pressure set up at this temperature, or butadiene with the catalyst in the propor tions specified for the discontinuous method, and if desired also the solvent, may be led at the reaction temperature and under pressure set up at this temperature over large-surfaced shaped packing. Residence periods of 10 to 20 minutes are usually sutficient, especially if the butadiene set free by the subsequent expansion is returned in circulation.
  • 1,5-cyclo-octadiene is obtained by the present process in at least as good a yield as in the known methods which are carried out in the presence of acetylene. In some cases, the yields are appreciably higher than in the known methods. It is not necessary to use glass-lined autoclaves and carefully to exclude moisture, so that the new process is far better suited to large-scale industrial operation than the known methods.
  • the favorable ratio of 1,5-cyclooctadiene to 4-vinyl-cyclohexene-(1) is also of advantage.
  • reaction products are valuable chemical intermediates, for example for the production of cyclo-octane and cyclo-octene which are important for the production of valuable polymers.
  • Example 1 For the preparation of the catalyst, 32.4 grams of nickel-bis-acrylonitrile are introduced while excluding air into a H. three-necked flask provided with a dropping funnel, stirrer and reflux condenser and suspended in about 500 ml. of absolute ether. 200 grams of triphenyl phosphite is added. The mixture is boiled under reflux for 8 hours with vigorous stirring. The initially intense red colored solution is discolored as the reaction proceeds. The product is filtered otf by suction while excluding air and washed with ether. After drying in an oil pump vacuum, 193 grams of a yellowish white finely crystalline substance is obtained which according to analysis has the formula:
  • Example 2 A mixture of 116 ml. (75.5 grams) of butadiene, ml. (66 grams) of n-hexane, 0.5 gram of hydroquinone and 5 grams of the nickel catalyst used in Example 1 is heated for twelve hours under a nitrogen pressure of 30 atmospheres gage at C. in a H. rotating autoclave of high-grade steel. After cooling, 155 ml. of liquid reaction product is obtained from which 36.5 grams of 1,5- cyclo-octadiene is obtained by fractional distillation over a circulating band column. 7.4 grams of 4-vinylcyclohexene-(l) and 8 grams of high-boiling constituents are isolated as byproducts. The conversion is thus 68.3 the selectivity 71% and the yield 49.5%. Investigation by gas chromatography shows however that a yield of 61% of the theory of 1,5-cyclo-octadiene is achieved.
  • Example 3 For the preparation of the catalyst, 11.2 grams of nickel-bis-acrylonitrile is introduced under nitrogen free from oxygen and water into a three-necked flask provided with a stirrer, reflux condenser and nitrogen inlet pipe, and suspended in 250 ml. of ether free from oxygen and water. 72 grams of tri-o-tolyl phosphite is then added. The mixture is boiled under reflux for 2 hours. The color of the originally red solution changes to yellow and the sediment passes into solution. The reaction mixture is then cooled for some hours in an ice-bath and the deposited crystals are filtered off by suction while excluding oxygen, washed with ether and dried in vacuo. 50.2 grams of lemon yellow crystals is obtained which upon heating in the air at C. are decomposed and which in the absence of air show discoloration above 120 C.
  • Example 4 1.5 grams of the catalyst described in Example 3, 0.2 gram of hydroquinone and 34.8 grams of decahydronaphthalene are charged into a 250-ml. pressure vessel. 35 grams of liquid butadiene is forced in and then the pressure vessel is heated for five hours at 120 C. while shaking. By working up as in Example 3, 65 grams of distillate and 3.2 grams of residue (catalyst and resin) are obtained. 25.8 grams of 1,5-cyclo-octadiene and 2.5 grams of 4-vinyl-cyclohexene-(1) can be detected in the distillate by gas chromatography. The conversion thus lies at 93.5%, the selectivity for 1,5-cyclo-octadiene at 82.5% and the yield at 77%.
  • Example 5 For the preparation of the catalyst, 51 grams of nickel()-bis-acrylonitrile and a solution of 293.5 grams of trithymyl phosphite in about 600 ml. of dioxane are introduced into a 14. three necked flask fitted with a stirrer and reflux condenser. While stirring, the temperature is raised to about 70 C., the nickel(0)bis-acrylonitrile, originally in suspension, passing into solution in the course of 1 to 2 hours. The yellow solution obtained is freed from any solid residues present by filtration and concentrated to about 250 ml. under reduced pressure. After cooling, the crystalline yellow substance is filtered off, washed with methanol and dried in a vacuum exsiccator.
  • the reaction product obtained in the autoclave (952 grams) is distilled at a pressure of 25 mm. Hg and a bottoms temperature up to 100 C. 16.7 grams of resin remains.
  • the distillate obtained is fractionated at normal pressure in a column packed with Raschig rings.
  • the fraction passing over between 80 and 131 C. contains, besides solvent, 7.0 grams of 4-vinyl-cyclo-hexene-(1), the fraction passing over from 131 to 149 C. (about 28 grams) consists of about equal parts of 4-vinyl-cyclohexene-(1) (13.77 grams) and 1,5-cyclo-octadiene (14.3 grams).
  • 431.3 grams of pure 1,5-cyclo-octadiene passes over between 149 and 151 C.
  • Example 6 For the preparation of the catalyst, 13.7 grams of nickel (0)-bis-acrylonitrile is caused to react with exclusion of air with a solution of 89.7 grams of tri-o-diphenyl phosphite in about 250 ml. of tetrahydrofurane in a 500-ml. three-necked flask fitted with a stirrer and reflux condenser. After stirring for about two hours at a temperature of 60 C., the nickel compound has practically completely passed into solution with a yellow color. Small amounts of residue are filtered off, the solvent is withdrawn under reduced pressure, the oily residue taken up with ether, filtered again and the ether evaporated. 90.3 grams of a foam which solidifies to form a yellow powder of low bulk density is obtained; according to analysis it has the composition:
  • the distillate contains, as may be ascertained by gas chromatography, 25.7 grams of 1,5-cyclo-octadiene and 1.4 grams of 4- vinyl-cyclohexcne-(l); the total yield, with reference to butadiene reacted, is 92% of 1,5-cyclo-octadiene, 5% of 4-vinyl-cyclohexene-(1) and 3% of resin; the mole ratio of 1,5-cyclo-octadiene to 4-vinyl-cyclohexene-(l) is 18.3:1. The conversion thus is 93%, the selectivity for 1,5-cyclo-octadiene 92% and the yield 86%.
  • Example 7 For the preparation of the catalyst, 2.6 grams of nickel(0)bis-acrylonitrile and 20.4 grams of tri-(2,4-ditertiary-butyl-phenyl) phosphite are reacted in about 150 150 ml. of dioxane while stirring at 60 to 70 C. The reaction is ended after one to two hours. A dark-colored solution is obtained. It is filtered, the solvent distilled off under reduced pressure and the oily residue obtained is taken up with ether. After filtering off the ether, 17.5 grams of a yellow-brown compound remains which according to analysis has the formula:
  • this contains 21.2% of 1,5-cyclo-octadiene and 9.2% of 4-vinyl-cyclohexene-(1). Accordingly, 10.8 grams of 1,5-cyclo-octadiene and 4.7 grams of 4-vinylcyclohexene-(l) have been formed. The selectivity is 60% for 1,5-cyclo-octadiene, the yield of 1,5-cyc1o-octadiene is 40.0%
  • Example 10 1.5 grams of bis-(tri-o-tolyl-phosphite)-nickel-monoacrylonitrile, 0.2 gram of anthraquinone and 57 grams of liquid butadiene are heated for twelve hours at 80 C. in a shaking autoclave of 250 ml. capacity. 50 grams of a red-brown liquid are obtained as reaction mixture. By distillation of this liquid, 43.3 grams of distillate are obtained which according to gas chromatographic analysis contains 87% of 1,5-cyclo-octadiene and 8.9% of 4-viny1- cyclohexene-(l). 4.5 grams of a brown oil remain as distillation residue.
  • Example 11 5.8 grams of the air-sensitive yellow complex bis-(trio-tolyl-phosphite -nickel-monoacrylonitrile ⁇ Ni (CH CHCN) ⁇ P (OC H CH -ortho is dissolved in 200 ml. of cyclohexane in a 1-l. threenecked flask. Gaseous butadiene is led under a gage pressure of about 150 mm. Hg at about 70 C. into the solution stirred by an impeller. The originally yellow solution turns red-brown. After leading in butadiene for about four hours, the solution is distilled at 15 mm. Hg and a bottoms temperature of 100 C. 141 grams of a colorless solution is obtained as distillate.
  • this contains 32.6% of 1,5-cyclo-octadiene and 3.5% of 4-vinyl-cyclohexene-(1). Accordingly, 5.0 grams of 4-vinyl-cyclohexene-(1) is formed besides 45.9 grams of 1,5-cyclo-octadiene.
  • Example 12 9.0 grams of nickel(0)-bis-acrylonitrile is mixed with a solution of 50.6 grams of tri- (a-naphthyD-phosphite in 200 ml. of dioxane while excluding air and then stirred at 60 to C. for 2% hours, the nickel(0)acrylonitrile slowly passing into solution.
  • the solution is filtered under nitrogen as protective gas.
  • the solvent is distilled off from the filtrate under reduced pressure and the oily residue is dissolved in 150 ml. of ether, the solution filtered and the solvent again distilled off. Taking up in ether, filtration and distilling off the ether are repeated twice.
  • the distillate (46.5 grams), as shown by gas chromatographic analysis, contains, besides the solvent, 17.8 grams of 1,5-cyclo-octadiene and 2.85 grams of 4- vinyl-cyclohexene-(l). The conversion is accordingly 81%, the selectivity in respect of 1,5-cyclo-octadiene 78.6% and the yield 63.6%
  • Example 13 4.35 grams of nickel(0)-bis-acrylonitrile is mixed with 20.9 grams of tri-(2,4-dimethylphenyl)-phosphite, dissolved in 100 ml. of tetrahydrofurane, at a temperature of 60 to 70 C. while excluding air. After stirring for two hours, the nickel(0)-bis-acrylonitrile has dissolved. The red-brown solution is filtered with exclusion of air and the solvent distilled off at 25 mm. Hg. A brown viscous residue (21.5 grams) is obtained. This is taken up in about 150 ml. of ether, filtered free from undissolved matter and the solvent distilled ofi. The treatment with ether is repeated twice. A solid residue remains behind.
  • Example 14 12.3 grams of nickel(0)-bis-acrylonitrile and 59 grams of tri-(3,5-dimethylphenyl)-phosphite (mole ratio 1:2) are reacted while excluding air at a temperature of 60 to 70 C. with continuous stirring, the nickel(0)-bisacrylonitrile passing completely into solution. The yellow-brown solution is filtered and the solvent competely 1 1 distilled off from the filtrate. The yellow residue is recrystallized from petroleum ether, 31.5 grams of a yellow crystalline compound being obtained which according to analysis is a bis-(tri-3,S-dimethyl(phenyl)-phosphite)-nickel()-monoacrylonitrile By working up the mother liquor, the yield of the complex may be increased.
  • Example 15 In a manner analogous to that described in Example 14, 11.9 grams of nickel(O)-bis-acrylonitrile is reacted with 68 grams or" tri-(p-tertiary-butylphenyl)-phosphite in 150 ml. of tetrahydrofurane at 60 to 70 C. for about 2 hours while stirring. The yellow solution is filtered, the solvent distilled oil? at 25 mm. Hg, the residue taken up in 150 ml. of ether, this solution filtered and the solvent withdrawn. 72.9 grams of nickel(0)-bis- (p-tertiary-butylphenyl)-phosphite is obtained.
  • a complex nickel catalyst which has been obtained by mixing in a diluent (A) an ester of phosphorous acid with (B) a complex compound consisting of 0-valent nickel in complex combination with an aliphatic organic compound selected from the group consisting of egg-ethylenically unsaturated aldehydes and a,,8-ethylenically unsaturated nitriles.
  • a process as claimed in claim 1 wherein said organic compound in complex combination with said 0-valent nickel is an u,B-ethylenically unsaturated aldehyde 3.
  • a process as claimed in claim 1 wherein said organic compound in complex combination with said 0- valent nickel is an a,fl-ethylenically unsaturated nitrile.
  • component (A) is the ester of the formula P(OR) wherein R represents a radical selected from the group consisting of alkyl of 1 to 12 carbon atoms, phenyl, naphthyl, and phenyl substituted by at least one substituent selected from the group consisting of alkyl of l to 12 carbon atoms, lower alkoxy, cyclohexyl, phenyl and chloro.
  • component (B) is nickel-bis-acrolein.
  • component (B) is nickel-bis-acrylonitrile.

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  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
US121362A 1960-07-07 1961-07-03 Production of 1,5-cyclo-octadiene from butadiene Expired - Lifetime US3219714A (en)

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DEB58507A DE1144268B (de) 1960-07-07 1960-07-07 Verfahren zur Herstellung von Cyclooctadien-(1, 5) aus Butadien

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US457183A Expired - Lifetime US3346608A (en) 1960-07-07 1965-05-19 Phosphite-containing nickel-(o)-complexes and method for their preparation

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DE (1) DE1144268B (en, 2012)
FR (1) FR1295072A (en, 2012)
GB (1) GB943697A (en, 2012)
NL (1) NL266664A (en, 2012)

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US3364273A (en) * 1966-02-23 1968-01-16 Columbian Carbon Cyclooligomerization using nickel (0) polydentate ligand
US3544643A (en) * 1968-01-27 1970-12-01 Hoechst Ag Process for the catalytic cyclo-dimerization of 1,3-diolefins
US4717775A (en) * 1984-12-28 1988-01-05 Union Carbide Corporation Transition metal complex catalyzed reactions
US20040260129A1 (en) * 2003-04-25 2004-12-23 Norbert Wilczok 6-(2,7-octadienyl)-1,4-cyclooctadiene

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DE1643071B1 (de) * 1959-12-22 1972-05-31 Studiengesellschaft Kohle Mbh Verfahren zur Cyclodimerisation von 1,3-Diolefinen
NL269313A (en, 2012) * 1960-09-17 1900-01-01
US3277099A (en) * 1962-07-28 1966-10-04 Basf Ag Production of open-chain oligomers of 1, 3-dienes
US3251893A (en) * 1962-12-31 1966-05-17 Nat Distillers Chem Corp Cycloolefin trimers
US3480685A (en) * 1963-03-20 1969-11-25 Nat Distillers Chem Corp Octatriene process
US3541177A (en) * 1967-03-15 1970-11-17 Japan Synthetic Rubber Co Ltd Process for the preparation of butadiene dimer
DE1643063B1 (de) * 1967-04-08 1972-03-16 Studiengesellschaft Kohle Mbh Verfahren zur Cyclodimerisation von 1,3-Diolefinen mittels Nickel enthaltender Katalysatoren
FR2021052A1 (en, 2012) * 1968-10-19 1970-07-17 Huels Chemische Werke Ag
US4012399A (en) * 1971-12-16 1977-03-15 Cincinnati Milacron Chemicals, Inc. Transition metal complexes with trivalent phosphorus compounds
US3846461A (en) * 1972-10-25 1974-11-05 Du Pont Process of preparing a zerovalent nickel complex with organic phosphorus compounds
JPS5198242A (en) * 1975-02-17 1976-08-30 Isopurentorimaano seizoho
DE2638430C3 (de) 1976-08-26 1981-04-23 Studiengesellschaft Kohle mbH, 4330 Mülheim Verfahren zur Herstellung von octatrienylierten Aminen bzw. von octadienylierten Schiffschen Basen
US4155925A (en) * 1978-02-16 1979-05-22 E. I. Du Pont De Nemours And Company Hexakis- and dihydridopentakis(phosphite ester)chromiums
US4416825A (en) * 1982-02-23 1983-11-22 E. I. Du Pont De Nemours & Co. Preparation of zerovalent nickel complexes
US4450113A (en) * 1982-08-09 1984-05-22 Borg-Warner Chemicals, Inc. Zerovalent nickel phosphite complexes
US4557809A (en) * 1985-04-12 1985-12-10 Borg-Warner Chemicals, Inc. Electrochemical synthesis of zerovalent transition metal organophosphorus complexes
DE19953058A1 (de) * 1999-11-03 2001-05-10 Basf Ag Phosphite

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US294575A (en) * 1884-03-04 Samuel h
US2686209A (en) * 1951-11-19 1954-08-10 Ici Ltd Production of cyclo-olefinic compounds
US2943116A (en) * 1957-05-08 1960-06-28 Du Pont Catalytic process for preparing 3, 5-and 3, 6-dimethylenecyclohexenes and monomeric and polymerized isomeric mixtures thereof
US2968665A (en) * 1959-03-12 1961-01-17 Du Pont Polyfluoroalkylbiphosphine-bis-(nickel tricarbonyl) compounds
US2972640A (en) * 1959-04-27 1961-02-21 Cities Service Res & Dev Co Cycloolefin production utilizing isobutylene or its dimerization product as catalyst activator
US2993065A (en) * 1956-10-24 1961-07-18 Interchem Corp Pigment and method of preparing same
US3152158A (en) * 1961-01-23 1964-10-06 Cities Service Res & Dev Co Method of preparing tetrakis (triorganophosphite) nickel compounds

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DE881511C (de) * 1950-09-12 1953-06-29 Ici Ltd Verfahren zur Herstellung von Cycloolefinen mit mindestens 8 Kohlenstoffatomen im Ring
DE951213C (de) * 1951-11-19 1956-10-25 Ici Ltd Verfahren zur Herstellung von Cycloocta-1, 5-dien durch Dimerisierung von Butadien
BE598298A (en, 2012) * 1959-10-06 1900-01-01

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US294575A (en) * 1884-03-04 Samuel h
US2686209A (en) * 1951-11-19 1954-08-10 Ici Ltd Production of cyclo-olefinic compounds
US2993065A (en) * 1956-10-24 1961-07-18 Interchem Corp Pigment and method of preparing same
US2943116A (en) * 1957-05-08 1960-06-28 Du Pont Catalytic process for preparing 3, 5-and 3, 6-dimethylenecyclohexenes and monomeric and polymerized isomeric mixtures thereof
US2968665A (en) * 1959-03-12 1961-01-17 Du Pont Polyfluoroalkylbiphosphine-bis-(nickel tricarbonyl) compounds
US2972640A (en) * 1959-04-27 1961-02-21 Cities Service Res & Dev Co Cycloolefin production utilizing isobutylene or its dimerization product as catalyst activator
US3152158A (en) * 1961-01-23 1964-10-06 Cities Service Res & Dev Co Method of preparing tetrakis (triorganophosphite) nickel compounds

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3364273A (en) * 1966-02-23 1968-01-16 Columbian Carbon Cyclooligomerization using nickel (0) polydentate ligand
US3544643A (en) * 1968-01-27 1970-12-01 Hoechst Ag Process for the catalytic cyclo-dimerization of 1,3-diolefins
US4717775A (en) * 1984-12-28 1988-01-05 Union Carbide Corporation Transition metal complex catalyzed reactions
US4737588A (en) * 1984-12-28 1988-04-12 Union Carbide Corporation Transition metal complex catalyzed reactions
US20040260129A1 (en) * 2003-04-25 2004-12-23 Norbert Wilczok 6-(2,7-octadienyl)-1,4-cyclooctadiene

Also Published As

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FR1295072A (fr) 1962-06-01
NL266664A (en, 2012) 1900-01-01
DE1144268B (de) 1963-02-28
US3346608A (en) 1967-10-10
GB943697A (en) 1963-12-04

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