Патент USA US2406632код для вставки
2,406,632 Patented Aug. 27, 1946 ; UNl-TED-’_ STA-res PATENT ‘ ‘2,406,632 PRODUCTION OF CYCLO-OLEFINIC "HYDRO CABBONS AND .AROMATIC @HYDROCAR _ BONS ‘Herman Pines and ‘Vladimir-"N. Ipatie?’, Chicago, 111., assignors v‘to ‘Universal Oil Products Com vfpany, ‘Chicago, 111., ‘a corporation of Delaware .No Drawing. .. Applica'tionDecember15,.1944, _‘ ' , , 1 , I‘Seri'a'l'No. 568,392 2 ' ' ‘ ' 5 essiproceeds ‘preferably with conjugated ‘dio‘l‘e?ns, of a monohydric alcohol with a conjugated di other diole?ns ‘are sometimes usable, ‘particularly when rearrangement occurs at ‘the conditions ‘of 'ole?nic hydrocarbon containing :at least 1i ‘carbon " - Another object of ‘this invention is ‘the pro duction of a cyclohexene/hydrocarbon by con; densing analkanol with a'oonjugated diole?n. A ‘further-object of this ‘invention is the pro duction of a cyclohexene hydrocarbon by the con densation of a conjugated diole?n with an alcohol selected from the group consisting of primary and secondary alkanols. alternate single and double bonds ‘including .two double bonds. Althoughthe reaction of ourproc ‘ An‘ object of this 'i'nvention'is the condensation atoms‘per molecule. . ess‘ contain ‘at ‘least :4 carbon ‘atoms per molecule and are preferably “conjugated ‘diole?ns in‘that each of said hydrocarbons contains a'system' of ole?ns by condensing a diole?nic Thydrocarbon having at least “4 carbon atoms'per molecule with , vDiole?n'ic hydrocarbons ‘utilizable in our proc invention ‘relates’ .to a ‘process for vproducing cyclo alcohol. ' _ f'l'hisjinvention relates to ‘a process ‘for produc ing cyclic hydrocarbons. More speci?pally,v the amonohydric ' 10 the reaction. ' ' ‘ , Monohydric alcohols utilizable also as starting‘ vmaterials ‘in vthe‘ process "of ‘our invention "are generally those of the;aliphatic-“seriesand ~‘pref erably are‘saturated’aliphatic carbinols which 15 are also known as alkanols. Alkanols which do not contain a quaternary carbon atom are par ticularly desirable for condensation with a di ole?nic hydrocarbon as herein set forth as al-_. kanols which contain a quaternary carbon atom A still further object of this invention is the production of 1,3,5-trimethylcyclohexene by con 20 sometimes yield a substantial proportion of a ter densing 2~methyl-1,3-pentacliene and isopropyl tiary ole?n rather than the condensation product alcohol. desired. One speci?c embodiment of this invention re Although our process issometimes carried out lates to a process for producing a cyclo-ole?n in the absence of an added catalyst at suitable op which comprises condensing an alkanol and a di erating conditions of temperature and pressure, ole?nic hydrocarbon having, at least 4 carbon we prefer to utilize certain catalytic materials atoms perv molecule in the presence of an acid to assist in vthe condensation of a diole?nic hy acting catalyst at a temperature of from about drocarbon and a monohydric alcohol. Catalysts 150° to about 400° C. so utilizable are acid-acting materials and com A further embodiment of this invention relates 30 prise activated alumina,‘ ‘hydrated silica, acid to a process for producing a benzene hydrocarbon which comprises condensing an alkanol and a conjugated diole?n to produce a cyclohexene hy treated clays; synthetically prepared composites including silica-alumina, silica-alumina-zirconia, alumina-zirconia, silica-alumina-thoria, etc.;. drocarbon, hydrogenating said cyclohexene hy acids such as hydrochloric acid, hydrobromic acid, drocarbon to a cyclohexane hydrocarbon, dehy 35 a phosphoric acid, sulfuric acid, or a heteropoly drogenating said cyclohexane hydrocarbon to a acid as phosphotungstic or phosphomolybdic acid; benzene hydrocarbon and hydrogen, and utilizing and also aqueous solutions of hydrolyzable salts at least a portion of said hydrogen in the hydro such as ferric chloride, magnesium chloride, zinc genation of said cyclohexene hydrocarbon. chloride, ammonium ‘chloride, magnesium acid cyclohexene and di?erent alkyl cyclohexene 40 phosphate, sodium acid sulfate, etc. These ma hydrocarbons which are obtainable by the process of our invention may be hydrogenated to cyclo terials which we employ as catalysts in our process are acid-acting in the sense that an aqueous solu hexane hydrocarbons or they may be dehydro tion or suspension thereof in water has a pH genated to benzene and alkyl benzene hydrocar .below 7. bons. 4.5 Our process may be carried out using either By the term “condensation” used inthis speci? batch or continuous types of operation, although cation and in the claims, we mean the chemical the latter is preferable. The process is carried combination of a diole?nic hydrocarbon having at out at a temperature of from about 150° to about least 4 carbon atoms per molecule and a mono 400° 0., but preferably at a temperature of from hydric alcohol accompanied by the splitting out 50 about 175° to about 300° C. The process may of water. Thus, 2-methyl-1,3-pentadiene and be conducted at atmospheric pressure but is pref isopropyl alcohol react at an elevated tempera erably effected at a superatmospheric pressure ture and preferably in the presence of an acid acting catalyst to produce 1,3,5-trimethylcyclo hexene and water as the principal products of the process. . which is generally not in excess of about 100 at mospheres. The following example is given to illustrate the character of results obtainable by the process 4 drocarbon which comprises condensing a diole ?nic hydrocarbon having at least 4 carbon atoms of our invention, although the example is not in troduced with the intention of restricting unduly per molecule with an alkanol at a temperature the broad scope of the invention. 1.6 molecular proportions of isopropyl alcohol of‘from 1; 3. A process about150° forto producing abouti400‘fa;CA. cycloiole?nic I _‘ v hy and l molecularrv proportion =‘of; Z-methyl-l?s drocarbon which comprises condensing a diole pentadiene are commlngled and charged to an autoclave containing a 5% by weight solution of _ ammonium chloride in Water. id-?nic hydrocarbon having at least 4 carbon atoms per molecule with an alkanol at a temperature of’ from about 150° to about 400° C. and at a the ammonium mixture of achloride diole?nic solution hydrocarbon-‘and is The about volume thatof'. iso-W of 10 pressure of from about 1 to about 100 atmos propyl alcohol introduced thereto. After the autoclave and contents are heated atabout 250° pheres. ? ' ' 4. A, process fornproducing a cyclo-ole?nic hy C. for 3 hours, the heating is discontinued and ‘ V - drocarbon which comprises condensing a diole the reaction mixture is permitted to 'cool.,,.After 15 drocarbon layer comprising 1,3,5-trimethylcyclo-=I'~jn cooling, the reaction mixture, contains an 113’ hexene in an amount corresponding to‘about " 35% of the theoretical yield based upon’ the di-, ' ole?n charged. ‘ ,JI'lie novelty and utility of theprocess of the 20 present invention are ‘evident from'the preceding speci?cation‘v and example, although neither sec tion is introduced to'lir'nit’unduly' the broad scope of our inventionljl ' ' '7‘ " ' ' ' , ‘?nic hydrocarbon having at least 4 carbon atoms per molecule with an alkanol in the presence of ‘an’ acid-‘acting catalyst at a temperature of from about 150° to about 400° C. _5. Aiprocess for producing a cyclo-ole?nic hy drocarbon which comprises condensing a diole ?nic hydrocarbon having‘ at least 4 carbon atoms per molecule with an, alkanol'in the presence of an acid-acting catalyst at a temperature of from about 150°‘ to about 400° C. and at a pressure of from about 1 to about 100 atmospheres. ‘ 6. A process for producing a cyclo-ole?nic hy drocarbon ‘which comprises condensing a conju will; process for producing'a cyclo-ole?nic hy gated diole?nic hydrocarbon with an alkanol in drocarbon which'compri'ses reacting a diolefinic the presence of an aqueous solution of a hydro hydrocarbon having at least 4 carbon atoms' per molecule and a monohy'dric alcohol at a sufficient , , lyzablei metal salt at a temperature of from’about 1' We claim as our invention! ‘ . ‘ temperature and pressure that condensation of said diole?m'c hydrocarbonua’nd monohydric al cohol is the principal reaction of theprocess. ZJA process jorproducing a cyclo-ole?nic hy 30 150° to about 400° C. and at a pressure of from about 1 to aboutlOO atmospheres. ' . HERMAN PINES. ‘ . VLADIMIR N. IPA'I'IEFF.