Патент USA US2406645код для вставки
Apg. 27, 1946. > c. L. THOMAS, y 2,406,645 ySYNTHESIS OF AROMATIC COMPOUNDS Filed sept. 2s,v 1944 wäh.w I /. K v NWN .0.0M_ QM.“ _ ONM; â - N mKN Patented Aug. 27, 1946 2,406,645 UNITE-D STATES .PATENT -oFFi-CE SYNTHESIS OFAROMATIC COMPOUNDS Gharles‘L.;Th'omas, Riverside,` Ill.„-assìgnor,tn1lni’ Y versal1Qil5I’roducts Company, Chicago, Ill., a '_corporationrof- Delaware Application ~September 28, 19.44, SerialìNo. 556,263 Y (01.;260-67-1) l»1li-.Claims l This invention relates‘to the> treatment of-= poly nuclear ‘aromatic compounds `'containing «a con -jugated dienefstructure -in 'a Diels-Alder--type re action. More particularly the present 'invention'is‘ di rected to the reaction fof Ipolynuclear »aromatic compounds comprising anthracene #and substi tution Àproducts thereof lwith an - unsaturated» hy drocarbon. _ Theftypical Diels-Alder reaction or dienesyn thesis, `_as it is also knoWnfinvolves-‘the 11,4‘addi 'tion of asys'tem of conjugateddoublebonds'to a compound known as -a -dienophile Aandcontaining an l“activated” ygroup ofthe type: -C=C`»--C'=O vor C~=-ïC-`C=O, -Although the--dienophile-isespe 15 cially, active ' When> 4the »- carbonyl ' group is present, '-the reaction -will halso occur Yif -o'ther substituent _groups replace »or Yaugment 'the `carbonyl »group >in the dienophilic compound. 'I‘hesesubs'tituent groups include acetoxyl, nitro, sulfonyl, cyano, amino, etc. The-present invention ‘dea‘ls'vwith the reactionlbetween polynuclear-«aromatics and sub- ' stitution products thereof, with unsaturated ïhy drocarbons in the absence of 'suchfï‘activatin groups. ~ « Broadly,'the present inventionßrelatesetoa proc ess which ’comprises thermally, -~ non-catalytically reacting an unsaturated hydrocarbon‘andfapoly nuclear Y'aromatic -‘compound Àcontaining a con jugated diene structure and'capable of-forming a 30 ‘bridge »between the carbon -atoms 'in v`the'L‘l lposi tions of the diene part of the molecule. In'one embodiment this îinvention Jrelates to a 4process which comprises thermally, `non-cat ~ alytically reacting ananthracene compound tcon taining a conjugated dienestructure `>with an vali phatic oleiin at a temperaturewithinlthe‘range of »about 100 to about-300i’ C. In another embodiment'my‘invention relates to 'a process Awhich comprises thermally, non-‘cat alytically reacting an'ant‘hra'cene compound con- ' The polycyclic aromatic hydrocarbons 'which are 'suitable for ‘the ¿present process include, in addition to -anthracen-e, V4benzanîtl'iracenes, tetra 35 cene, 'pentacene, hexacene, dibenzan'thracenes, Vchrysene, Ycholanthrene, 1naphthacene and Vtheir substitution products including alkyl, alkoxyl,'=hydroXyl, amino,íha-logenand~nitro derivatives. (All of these »contain .one Yor «more conjugated dienic 40 structures.) Anthraquinone and 9,10-dihydro anthracene derivatives are not substituted an taining a conjugated diene'structurewith’a cyclic thracenes land .are :not jincluded ini/this ¿group o1e1’1`.n«at'a> temperatureNwithin theerange of about .which ¿comprises onlyipolynuclear aromaticsf con ~100ito about 300°' C. taining .a „conj ugated l,diene structure. The reactions of my invention may-jbe "illustrat 45 The unsaturated -compounds vwhich fare. reacted >ed "by the 'following »equations which show the 'with .the ¿anthracene :hydrocarbons »comprise compositions formed when anthracene i«is 1reacted mono-,oleñnsfsuchfas;ethy1ene,3propylene, ,1- and -with ‘an aliphatic olefin and va Ecyclo-olefin, re spectively. ,fZ-butylenes, «isobutylenean-d the likefueither alone, ïadmixed :or `mixed Y@in non-,reactive substances. 50 Dioleñn .hydrocarbons which maybe used lin cludesallene, butadiene, piperylene, isoprene, v.di allyl, ¿eta -Cyclo-.oleñns l«such ¿as cyclopentene, cyclohexene, cycloheptene, .-etc„ .and the Lcorre sponding -fcyclodienes 'are falso «suitable for the process. :Acetylenics'compoundsromprisingeither aliphatic ,hydrocarbons oriaromatichydrocarbons 2,406,645 3 having acetylenic side chains may also be used. No catalyst is employed in this reaction which takes place at temperatures from about 100° to ing a bridge between the carbon atoms in the 1,4 v positions of the diene part of the molecule. 2. A process which comprises thermally, non catalytically reacting an oleñnic hydrocarbon with about 300° C.` The reaction can be effected in the presence or absence of a solvent and can take place in a batch type operation, as for example a polynuclear aromatic compound containing a conjugated diene structure and capable of form in an autoclave, or in a continuous manner by ing a bridge between the carbon atoms in the conducting the reactants through the reaction zone. 1,4 positions of the diene part of the molecule Pressures below 2000 pounds per square inch are generally satisfactory. at a temperature within the range of about 100 to about 300° C. 3. A process which comprises thermally, non - The following examples illustrate the reaction comprising my invention but should not be con catalytically 'reacting an oleñnic hydrocarbon strued as unduly limiting the invention in accord-ance therewith. with a substituted polynuclear aromatic com 15 pound containing a conjugated diene structure Eœample I and capable of forming a bridge between the carbon atoms in the 1,4 positions of the diene part of the molecule at a temperature within the range of about 100 to about 300° C. 4. A process which comprises thermally, non catalytically reacting an olefinic hydrocarbon with a polynuclear aromatic compound containing three benzene rings and having a conjugated diene structure and capable of forming a bridge be tween the carbon atoms inthe 1,4-positions of the diene part of the molecule. 5. A process which comprises thermally, non catalytically reacting anthracene with an oleñnic hydrocarbon at a temperature within the range 100 grams of anthracene was placed in an auto clave and the vessel closed. Ethylene was added to a pressure of 50 atmospheres and the tern perature raised to 200° C. Ethylene was slowly absorbed. AUpon cooling and opening the auto clave, a somewhat impure product was removed which melted at 140° to 141° C. Unreacted an thracene was also found to be present. 130 grams of toluene was added as a solvent and the auto clave again closed, pressured to 50 atmospheres with ethylene and heated to 200° C. Again eth ylene was absorbed. The reaction product was removed from the bomb and crystallized from the of about 100 to about 300° C. toluene followed by recrystallization from alco 30 hol. The product which comprised 9,10-ethano , « . 6. A process which comprises thermally, non -catalyticallyrreacting an oleñnic hydrocarbon with a polynuclear aromatic compound containing 9,10-dihydroanthracene was in the form of white needle-like crystals which melted at 142° to 153° C. and which boiled at atmospheric pressure with out noticeable decomposition. An analysis of the three benzene rings and having a Vconjugated diene structure and capable of forming a bridge .between the carbon atoms in the 1,4 positions i of the diene part~of the molecule at a tempera-‘ ture within the range of about 100 to about anthracene-ethylene reaction product showed that it comprised 93.12% carbon and 6.71% hy drogen, while the calculated percentages of carbon and hydrogen for 9,10-ethano-9,l0-dihydroanthracene were 93.20 and 6.8 respectively. 4 conjugated diene structure and capable of form-, 300° The 40 Í C.- » - _ Y 7. A process which comprises thermally, non catalytically reacting anthracene with an aliphatic reaction product did not form a picrate, indicat ing that it no longer contained the normal an vole?ìn at a temperature within the range of about thracene structure. -100 to about 300° C. catalytically reacting anthracene with a mono oleñn at a temperature within the range of about „100 to about 300° C. 9. A process which comprises thermally, non 100 grams of anthracene was placed in a re-V action vessel to which was added 1000 cc. of cycloheXene. ' 8. A process which comprises thermally, non Example II The mixture was heated to 250° C. for eight hours. A solid product was formed' " lcatalytically reacting anthracene with a cyclic ole which was recrystallized to remove unreacted an 50 ñn at a temperature within »the range of about 100 to about 300° C. thracene. Two isomers of 9,10-cyclohexano-v 10. A process which comprises thermally, non v,catalytically‘ reacting anthracene with an unsat 9,10-dihydroanthracene, one melting at 145-149“ C. and the other at,159-160° C. were found on analysis to comprise carbon and hydrogen as fol-`Y lows: (l) 92.51% carbon and 7.42% hydrogen and (2) 92.39% carbon and ’7.59% hydrogen. The calculated values for the reaction product were 92.31 % carbon and ’7.6% hydrogen. Example III Íurated hydrocarbon in the presence of an unre active solvent at a temperature within the range y of about 100 to about 300° C. 11. A process which comprises thermally, non Acatalytically'reacting anthracene with a mono _olefinic hydrocarbon in the presence of a non 60 polar hydrocarbon solvent> at a temperature with in the range of about 100 to about 300° C. 12. A process which comprises thermally, non Ultraviolet absorption spectra for the ethylene adduct and for the cycloheXene-anthracenere catalytically reacting anthracene with ethylene action products, the latter prepared according to p at a temperature within the range of about 100 the procedure of Example II, are shown on the' to about 300° C. in the presence of a solvent com 65 accompanying figure. The spectra were obtained prising toluene. *by means of a Beckman Quartz spectrophotom 13. A process which com-prises thermally, non eter, following the standard procedure for this catalytically reacting anthracene with cyclohex instrument. As shown on the graph the absorp tion spectra of the ethylene-anthracene and>` cyclohexene-anthracene reaction products are very similar to that of 9,10-dihydroanthracene. I claim as my invention: l; A process which comprises thermally, non ' catalytically reacting an oleñnic hydrocarbon with -a polynuclear aromatic compound containing a ene at a temperature within the range of about 100 to about 300° C. in the presence of a solvent comprising toluene. ' . ’ 14. The :compound `~9,10-cyclohexano-9,10¿di hydroanthracene. „ , , . CHARLES L. THOMAS. 7.5 Certificate of Correction Patent No. 2,406,645 ' " August 27, 1946 CHARLES L. THOMAS It is hereby certified that error appears inthe printed specification of the above numbered patent requiring correction as follows: Column 3, lines 33 and 34, for “142° to 153°;` C.” read 142° to 143° 0.; and that the said Letters Patent should be read afs corrected above, so that the same may conform to the record of the case in the‘ï-,Patent Oíîìce.~ ~ Signed and sealed this 24th day of April, A. D. 195.1. [SEAL] THOMAS F. MURPHY, Assistant ó'ofmm'ssz'oner of Patents.