US3336406A - Preparation of polymethyladamantanes - Google Patents

Preparation of polymethyladamantanes Download PDF

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US3336406A
US3336406A US486307A US48630765A US3336406A US 3336406 A US3336406 A US 3336406A US 486307 A US486307 A US 486307A US 48630765 A US48630765 A US 48630765A US 3336406 A US3336406 A US 3336406A
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hcl
bridgehead
reaction
temperature
perhydroaromatic
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US486307A
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Schneider Abraham
Hills Overbrook
Edward J Janoski
Roy W Mcginnis
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Sunoco Inc
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Sun Oil Co
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Priority to US486307A priority Critical patent/US3336406A/en
Priority to GB20938/66A priority patent/GB1106809A/en
Priority to NL6609427A priority patent/NL6609427A/xx
Priority to DE19661593399 priority patent/DE1593399C3/de
Priority to FR75520A priority patent/FR1499313A/fr
Priority to BE686687D priority patent/BE686687A/xx
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
    • C07C5/22—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by isomerisation
    • C07C5/27—Rearrangement of carbon atoms in the hydrocarbon skeleton
    • C07C5/2702—Catalytic processes not covered by C07C5/2732 - C07C5/31; Catalytic processes covered by both C07C5/2732 and C07C5/277 simultaneously
    • C07C5/271—Catalytic processes not covered by C07C5/2732 - C07C5/31; Catalytic processes covered by both C07C5/2732 and C07C5/277 simultaneously with inorganic acids; with salts or anhydrides of acids
    • C07C5/2718—Acids of halogen; Salts thereof; complexes thereof with organic compounds
    • C07C5/2721—Metal halides; Complexes thereof with organic compounds

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  • any perhydroaror fif gi fi gf g 3523122 3 fi s g gg g Plum 5 matic hydrocarbon which has three rings and from twelve Filed Sept. 10, 1965, Ser. No. 486,307 to fourteen carbon atoms lHClllSlV8 can be used.
  • any such per- C -C tricyclic perhydroaromatic hydrocarbons to prohydroaromatic hydrocarbon will readily isomerize under prise polymethyladamantanes. More particularly the inthe conditions herein specified to form a product having vention concerns the conversion of such perhydroaromatic an adamantane nucleus and methyl substituents located hydrocarbons into adamantanes having the same number at bridgehead positions. Since the nucleus has ten carbon of carbon atoms and from two to four methyl groups at- 15 atoms, the product will have from two to four carbon tached to bridgehead carbon atoms of the adamantane atoms in excess of those required for forming the nucleus, nucleus.
  • bridgehead polymethyladamantanes predepending upon the particular perhydroaromatic selected pared according to the invention are the following: 1,3- as starting material. These excess carbon atoms will all dimethyladamantane; 1,3,5 trimethyladamantane; and appear as methyl groups located at bridgehead positions 1,3,5,7-tetramethyladamantane. in the final isomerization product.
  • ADAMANTANE ADAMANTAN E carried to completion, the ultimate product is mainly a polymethyladamantane having two or more methyl groups attached to bridgehead carbon atoms of the a-damantane nucleus.
  • the isomerization reaction proceeds slowly and an undesirably long reaction time is required to attain the maximum yield of the bridgehead polymethyl isomers. Merely raising the reaction temperature to above the 50 C.
  • the present invention constitutes an improvement over the process of United States Patent No. 3,128,316, whereby bridgehead polymethyladamantanes of the C -C range are produced from C -C tricyclic perhydroaromatics in a considerably more rapid reaction.
  • the tricyclic perhydroaromatic charge is contacted at a temperature in the range of 55150 0., preferably 70-120 C., and in the presence of free HCl maintained at -a partial pressure of at least 0.1 psi. with a pre-formed aluminum chloride catalyst complex.
  • the catalyst is a liquid complex previously prepared by reacting AlCl HCl and paraffin hydrocarbon having at least seven carbon atoms per molecule as hereinafter described.
  • non bri-dgehead as used herein in referring to a product is meant that at least one of the substituents is attached to the adamantane nucleus at a n0nbridgehead carbon atom.
  • the total amount of these at equilibrium generally is less than 10%, so that 1,3-DMA is by far the predominant product resulting from complete isomerization of perhydroacenaphthene.
  • an intermediate isomerization product again is formed in which ethyl substituents are located at bridgehead and non-bridgehead positions.
  • the intermediate isomers also contain, in addition to the ethyl group, a methyl group which may be attached at bridgehead or non-bridgehead positions. Further isomerization converts the ethyl group to two methyl groups and shifts non-bridgehead methyl groups mainly to bridgehead positions.
  • T MA 1,3,5 trimethyladamantane
  • the present process involves the use in the isomerization zone of free hydrogen chloride in combination with a catalyst which is a pre-formed liquid complex obtained by reacting AlCl HCl and paraffinic hydrocarbon as described below.
  • the catalyst should contain suspended therein an excess of AlCl over that which reacts to form the complex.
  • the isomeriation is conducted by contacting the hydrocarbon charge at a temperature of 55-150 0., preferably 70-120 0., with the catalyst which constitutes a separate liquid phase in the reactor.
  • Gaseous HCl is added to the reactor in order to maintain therein a partial pressure of HCl of at least 0.1 pound per square inch (p.s.i) and more preferably at least 1.0 p.s.i.
  • HCl partial pressure in the range of 1-30 p.s.i. is typical but a much higher HCl pressure, e.g., 100500 p.s.i., can be employed without any adverse effect.
  • HCl pressure in the range of 1-30 p.s.i. is typical but a much higher HCl pressure, e.g., 100500 p.s.i., can be employed without any adverse effect.
  • These values refer to partial pressure of the HCl as measured at the tempera ture at which the reaction is conducted.
  • the mixture is continuously agitated to etfect initimate contact between the phases.
  • the isomerization reaction takes place at an accelerated pace, proceeding to and through the ethyl intermediate stage and producing the desired bridgehead polymethyladamantane in high concentration.
  • Some amount of cracking occurs during the reaction, resulting in the formation of small amounts of lower boiling products such as isobutane, isopentane and naphthenes of the C C range. Nevertheless the activity of the catalyst is not substantially reduced as long as free HCl at a partial pressure above 0.1 p.s.i. is maintained in the reaction zone.
  • FIG. 1 graphically illustrates this rapid exothermic reaction.
  • FIG. 1 is for the isomerization of perhydroacenaphthene and shows the temperatures of the hydrocarbon reactant and of the fluid heating medium as a function of time from start-up.
  • the procedure employed was as follows: At room temperature perhydroacenaphthene and a pre-formed AlC -HCl-hydrocarbon complex catalyst were charged to a reactor and gaesous HCl was admitted thereto to a pressure of about 25 p.s.i.g.
  • the reactor had a jacket through which the fluid heating medium was continuously circulated and also was provided with a stirrer for intimately contacting the hydrocarbon and catalyst phases.
  • the run was begun by starting the stirrer and by continuously pumping the heating medium through the jacket while heating it in a preheater to raise the temperature.
  • the temperatures of the incoming heating medium and of the hydrocarbon reactant were continually measured, and the two curves of FIG. 1 show the respective values obtained as against time.
  • the temperature of the hydrocarbon reactant lags behind that of the heating medium in the initial heat-up period and for a time increases at more or less the same rate as the heating fluid tmeperature increases.
  • a strong exothermic reaction sets in, causing the hydrocarbon temperature to rise sharply above that for the heating medium.
  • This reaction corresponds to the conversion of the perhydroacenaphthene to the adamantane structure and it mainly produces ethyladamantanes.
  • the isomerization then slows down, as evidenced by the fact that the hydrocarbon temperature soon drops back toward that of the heating medium.
  • AlCl is suspended in a paraffin hydrocarbon or mixture of paraflins having at least seven and preferably eight or more carbon atoms per molecule and gaseous HCl is passed into the mixture.
  • gaseous HCl is passed into the mixture.
  • isoparatfins such as highly branched octanes, nonanes or decanes for this purpose but straight chain paraffins can also be used.
  • the reaction of the AlCl HCl and paraffin hydrocarbon can be effected at room temperature, although the use of an elevated temperature such as 50100 C. generally is desirable to increase the rate of reaction. For best results at least five moles of the paraffin per mole of AlCl should be employed.
  • the preformed catalyst prepared as described above and the tricyclic perhydroaromatic charge are introduced into a reaction zone and gaseous HCl is added thereto to maintain the HCl partial pressure as above specified.
  • the proportion of catalyst complex to perhydroaromatic charged is not critical but it is usually desirable to employ a weight ratio of complex to hydrocarbon of at least 1:10. More preferably such ratio is at least 1:1 and considerably larger ratios, e.g., 10:1, can be used if desired.
  • the reactor should be provided with means for agitating the mixture so as to effect good contact between the catalyst and hydrocarbon phases. Increases in the catalyst to hydrocarbon ratio and in the degree of agitation tend to expedite the reaction.
  • the bridgehead polymethyladamantanes are prepared in still higher concentrations, for example, in a purity of 95% or better.
  • the tricyclic perhydroaromatic charge is first reacted at a temperature of 55150 C., preferably 70120 C., and under an HCl pressure, all as above described. This produces an equilibrium product of polymethyladamantanes comprising mainly bridgehead products but also a minor but substantial amount of nonbridgehead polymethyl isomers.
  • the temperature is then dropped to within the range of 050 C. and preferably below 30 C. and contacting of the hydrocarbon and catalyst phases is continued. This results in the formation of a new equilibrium mixture in which the proportion of bridgehead to non-bridgehead isomers is substantially increased.
  • Table I specifically illustrates the benefit that can be derived by this procedure of following the higher temperature isomerization step with a further step for equilibrating at lower temperature.
  • Table I shows measured equilibrium values obtained for C adamantanes for equilibration at relatively high and relatively low temperatures, specifically, 83 C. and 27 C., by means of the AlCl complex catalyst.
  • Example 1 An AlCl complex catalyst was prepared by reacting 40 ml. of 2,2,5-trimethylhexane with 15 g. of AlCl at 65-75 C. while bubbling HCl into the mixture. After essentially all of the A101 had reacted, the mixture was cooled and allowed to stratify, and the excess hydrocarbon was decanted. The catalyst layer was washed with 30 ml. of 2,2,5-trimethylhexane and then was blown at room temperature with nitrogen to remove any excess HCl.
  • a shaker bomb was charged with 10.5 g. of the so-prepared complex, 5.0 g. of uncomplexed A101 and 11.0 g. of perhydroacenaphthene.
  • the latter was a mixture of four isomers produced by hydrogenating acenaphthene employing a Raney nickel catalyst.
  • the bomb was immersed in a water bath which had been heated to C. With the bath maintained at such temperature the bomb was agitated for 177 minutes. Small samples of the hydrocarbon phase were taken at times of 60, 117 and 177 minutes for analysis by vapor phase chromatography. After the third sampling the mixture was cooled to 0 C.
  • FIG. 2 the values listed in Table II for the contents of l-ethyladamantane and 1,3-dimethyladamantane have been plotted against reaction time.
  • Reference to FIG. 2 shows that without free HCl l-ethyladamantane quickly formed and that it constituted over one-half of the reaction product when a one-hour reaction time was reached. However further conversion of this isomer did not then occur and its content remained steady at about 56%.
  • a slow formation of the 1,3-dirnethyl isomer occurred as shown in Table II but this evidently was derived mainly through isomerization of the non-bridgehead dimethyl isomers and not l-ethyladamantane.
  • FIG. 2 further shows that when an HCl pressure was applied to the reaction zone, the ethyladamantane isomerized rapidly and the yield of 1,3-dimethyladamantane increased sharply. This illustrates the importance of using free HCl in the reaction zone in practicing-the present invention.
  • Example 2 perhydroacenaphthene was isomerized generally the same way as in the preceding example except that free HCl was used initially in amount equivalent to 10 p.s.i. measured at 0 C. (about 13.3 p.s.i. at the reaction temperature).
  • the bomb contained 14.2 g. of the A101 complex, 5.0 g. of uncomplexed AlCl 14.8 g. of a mixture of the four perhydroacenaphthene isomers and the free HCl.
  • the reaction temperature was about 89 C. Compositions of product corresponding to three reaction times as shown in Table III.
  • Example 3 A comparative run was made with free HCl under the conditions described in Example 2 except that the reaction temperature was maintained at about 42 C. instead of 89 C. Results are shown in Table IV.
  • FIG. 3 shows the 1,3-dimethyladamantane content of the products of Examples 2 and 3 as a function of reaction time. A comparison of the two curves shows the importance of reaction temperature in obtaining a high yield of the bridge-head dimethyl isomer within a reasonable reaction time. This figure considered together with FIG. 2 shows that both an elevated temperature and presence of free HCl, as herein specified, are important for achieving the desired results.
  • any C tricyclic perhydroaromatic can readily be isomerized to 1,3,5-trimethyladamantane and any C tricyclic perhydroaromatic can likewise be converted to 1,3,5,7-tetramethyladamantane.
  • Method of preparing polymethyladamantane of the C -C range in which the methyl groups are located at bridge-head positions of the adamantane nucleus which comprises contacting a tricyclic perhydroaromatic having 12-14 carbon atoms at a temperature in the range of 55-150 C. and in the presence of free HCl at a partial pressure of at least 0.1 p.s.i. with a pre-formed liquid complex obtained by reacting AlCl HCl and a paraflin hydrocarbon having at least seven carbon atoms and continuing said contacting under the conditions specified until at least a major portion of the tricyclic perhydroaromatic has been converted to said bridgehead polymethyladamantane.
  • Method of preparing polymethyladamantanes of the C -C range in which the methyl groups are located at bridgehead positions of the adamantane nucleus which comprises contacting a tricyclic perhydroaromatic having 12-14 carbon atoms at a temperature in the range of 55-150" C. and in the presence of free HCl at a partial pressure of at least 0.1 p.s.i.
  • Method of preparing 1,3-dimethyladamantane in high purity which comprises contacting a C tricyclic perhydroaromatic at a temperature in the range of 55- C. and in the presence of free HCl at a partial pressure of at least 0.1 p.s.i. with a pre-formed liquid complex obtaining by reacting AlCl HCl and paraffin hydrocarbon having at least seven carbon atoms until a major portion of the tricyclic perhydroaromatic has been converted to mixed dimethyladamantanes including a minor amount of the 1,2- and 1,4-isomers, reducing the temperature of the reaction mixture to within the range of 050 C. and continuing the contacting at said temperature of 0-50 C. until said amount has been substantially reduced by isomerization thereof to 1,3-dimethyladamantane.

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  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
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  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
US486307A 1965-09-10 1965-09-10 Preparation of polymethyladamantanes Expired - Lifetime US3336406A (en)

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Application Number Priority Date Filing Date Title
US486307A US3336406A (en) 1965-09-10 1965-09-10 Preparation of polymethyladamantanes
GB20938/66A GB1106809A (en) 1965-09-10 1966-05-11 Preparation of polymethyladamantanes
NL6609427A NL6609427A (enrdf_load_html_response) 1965-09-10 1966-07-06
DE19661593399 DE1593399C3 (de) 1965-09-10 1966-07-22 Verfahren zum Herstellen von PoIymethyladamantanen durch Isomerisieren tricyclischer perhydroaromatischer Kohlenwasserstoffe mittels eines AICI tief 3 -HCI-Paraffinkohlenwasserstoff-Komplexkatalysators
FR75520A FR1499313A (fr) 1965-09-10 1966-09-07 Fabrication de polyméthyl adamantanes
BE686687D BE686687A (enrdf_load_html_response) 1965-09-10 1966-09-09

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3437701A (en) * 1967-11-30 1969-04-08 Atlantic Richfield Co Alkyl adamantanes

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3128316A (en) * 1962-08-07 1964-04-07 Sun Oil Co Reaction of tricyclic perhydroatromatic hydrocarbons
US3258498A (en) * 1964-07-14 1966-06-28 Sun Oil Co Preparation of nitroalkyladamantanes

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3128316A (en) * 1962-08-07 1964-04-07 Sun Oil Co Reaction of tricyclic perhydroatromatic hydrocarbons
US3258498A (en) * 1964-07-14 1966-06-28 Sun Oil Co Preparation of nitroalkyladamantanes

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3437701A (en) * 1967-11-30 1969-04-08 Atlantic Richfield Co Alkyl adamantanes

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FR1499313A (fr) 1967-10-27
DE1593399A1 (de) 1970-07-30
DE1593399B2 (de) 1975-10-16
GB1106809A (en) 1968-03-20
NL6609427A (enrdf_load_html_response) 1967-03-13
BE686687A (enrdf_load_html_response) 1967-03-09

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