Патент USA US2404120код для вставки
Patented July 16, .1946 l '- 2,404,120 UNITED STATES PATENT. OFFICE " PRODUCTION OF AROMATIC DERIVATIVES William N. Axe, Bartlesville, Okla, assignor to Phillips Petroleum Company, a corporation of Delaware No Drawing. Application July 3, 1944, Serial No. 543,421 12 Claims. ~ (01. zed-e71) This invention relates to derivatives of aro~ '‘ matic compounds. In one modi?cation it relates to alkenyl derivatives of aromatic compounds. In another ‘modi?cation it relates to normal al kyl derivatives of aromatic compounds. As spe~ ci?c modi?cations it relates to the alkenylation of aromatic hydrocarbons and to the production ' of normal alkyl derivatives of aromatic hydro carbons. This application is a continuation-in part of my copending application Serial No. 433, 10 192, ?led March 3, 1942. 2 boiling normal l,3-tdiole?nys to produce normal monoalkenyl derivatives of said aromatic hydro carbons. ' 4 , Still another‘ object of this invention is to pro duce normal butyl benzene. Further objects and advantages of my inven tion will become apparent to one skilledin the art from the accompanying disclosure and dis cussion. . I have now found that aromatic compounds, includingr aromatic hydrocarbons, phenols, naph Normal alkenyl aromatic compounds and nor mal alkyl aromatic compounds are’ valuable in thols, and aromatic halides, can be reacted with normal 1,3-diole?ns to produce alkenyl deriva termediate compounds both in their own rights tives of said aromatic compounds. I have. fur and as intermediates in organic syntheses. They 15 ther found that such alkenyl ‘derivatives include may be used for the production of normal ali normal monoalkenyl derivatives whichcanv ‘be phatic derivatives of such compounds as amino successfully subjected. to nondestructive , hydroqe benzenes, aminonaphthalenes, phenols, naph-v thols, aminophenols, aminonaphthols, quinolines, genation to produce thecorrespondingnormal alkyl derivatives. 1 have .further discovered. that and the like. These materials can be used in the such derivatives can be‘produced in extremely highyields ,and can be recovered in substantial quantities in a condition of high purity. As the aromatic reactant of my process I prefer to use preparation of oxidation inhibitors, pharmaceu ticals, dyestuffs, and explosives. ‘The develop ment of the full potentialities of normal aliphatic derivatives of such compounds has been preclud benzene, naphthalene, simple alkyl derivatives of ed by the absence of suitable sources of such 225 these hydrocarbons such as toluene, ethylben compounds. Thus, when ole?ns are used to al zene, xylenes, and'the like, phenol, naphthols, ~ kylate aromatic compounds the normal alkyl de and simple alkyl derivatives of these materials, rivative is produced only in the case of ethylene and aromatic halides such as phenyl chloride, and with other ole?ns it is impossible to produce phenyl bromide, one of the naphthyl chlorides. a normal alkyl derivative by catalytic alkylation. 30 and the like, although other alkenylatable aro Synthetic methods for the production of normal matic compounds are notto be excluded from the alkyl derivatives have been limited heretofore to broad concept of my invention.‘ As the diole?n reactions of the Wurtz-Fittig type in which aro~ reactant I prefer to use a low-boiling normal, ‘1,3 matic halides have been condensed, in the .pres diole?n such as 1,3-butadiene, l,_3-pentadiene, ence of a metal such as sodium, with normal a1 35 1,3-hexadiene, and the like. Although it is a pri kyl halides. The best yields reported for such re mary object of my invention to produce normal actions have not exceeded about 30‘per cent of aliphatic derivatives by the use of normal l,3-di_ the theoretical yield and more often actual ole?ns, it is to be understood that alkyl deriva _ yields are from about 10/to 20 percent of the tives of normal 1,3-diole?ns, such as S-methyl theoretical yields. Other disadvantages of such 40 l,3-hexadiene and 6-methyl-l,3-heptadiene, to synthesis operations include the use of large produce aromatic derivatives such ‘as l-phenyl quantities of metals ‘such as sodium with appre G-methyl heptylene, andthe like, are not to be ciable attendant hazards, the employment of ex excluded from the broad concepts of my inven pensive intermediate compounds, the necessity of special solvents, and the relatively di?icult pro 45 ~ Broad'features of this process may be more duction of. normal alkyl halides readily understood by considering a typical pro An object of this invention is to produce nor cedure. A blend of butadiene in benzene, in mal aliphatic derivatives of aromatic compounds. ‘ which the benzene is present in substantial mo Another object of this invention is to produce lar'excess, serves asthe primary feed stock. The normal alkyl derivatives,v of aromatic compounds. blend is charged to a reaction zone at moderate A further objectyof this invention is to produce temperatures and pressures where it is intimate normal alkenyl derivatives of. aromatic com ly commingled with a’ liquid complex compound of boron fluoride such as those to be hereinafter A still further object of this invention is to re described. The e?'luent is preferably continuous tion. pounds. , . ‘ , " . ' » act low-boiling aromatic hydrocarbons-with 10w: ly removed from the reaction zone and afterpme: 2,404,120 . , . 4 3 chanical separation of the catalyst phase, the preferable not to use a granular material contain hydrocarbon stream is washed free of dissolved ing appreciable amounts of silica. boron ?uoride and the excess benzene is recoV-. In the alkenylation step the reaction appears to be primarily mono-alkenylation to form mono alkenyl derivatives of the aromatic compound. It also appears that secondary reactions take place ered by fractional distillation. The debenzenized product is further fractionally distilled to sepa-‘ rate a main product (normal butenyl benzene, or. phenyl butene) boiling at about 365‘to about 370° ' to certain extents,‘ including cyclization and/or polymerization of the resulting monoalkenyl F., and a higher-boiling kettle product. The ‘ main product fraction may be hydrogenated over derivatives. This conclusion is based on the ob servation that the aromatic compound reacted is a conventional hydrogenation catalyst such as‘ molecularly equivalent to the diole?n reacted. If extensive polyalkenylation occurred, to form di ;or tri-alkenyl aromatic derivatives, the amount Raney nickel, platinum or any of the .morerugged industrial hydrogenation catalysts to yieldln-bu-l tylbenzene, which ordinarily requires ‘no further of aromatic hydrocarbon reacted would be sub I have found that efficient catalysts for such 15 stantially less than the molecular equivalent'of the diole?n, while if the monoalkenyl derivative alkenylation reactions can be prepared by sub-v entered into reaction with the aromatic hydro stantially saturating water with a boron trihalide. puri?cation. 7 carbon, to form the corresponding di-substituted A preferred boron trihalide is boron trifluoride, para?in hydrocarbon, the amount of aromatic hy although I do not intend to exclude other boron trihalides, particularly ‘boron trichloride and 20 drocarbon reacted would be substantially greater than .a molecular equivalentof the diole?n. No boron tribromide which are low-boilingmaterials. appreciable polymerization of- the diole?n is be A preferred catalyst for use in myprocess is con lieved to take place under preferred conditions veniently prepared bypassing gaseous boron ?uo ride into water until the desired hydrate concen tration is realized. The resulting hydrate is aliq uid of relatively high speci?c gravity and sub stantially immiscible with hydrocarbons. . Dur ing this reaction considerable heat is evolved and suitable means for cooling should be provided. Since the speci?c gravity of a completely satu rated solutionis approximately 1.77, convenient, control of concentration can'be effected by means of hydrometer determinations. Means for‘ me » chanicalagitation of the absorbent liquid may be used, andIhaJyefouhd that such means are often helpful in obtaining some of the higher concentra- ' ' ,tions of the hydrate used in the process. In the vpreparation of the catalyst, the gaseous boron ?uoridemay be passed into waterwhilethe tem of operation, a conclusion deducedfrom a con sideration of. the relativeamounts of reactants which undergo reaction and from the characteris tics of such ‘high-boiling products. Such results contrast with the results obtained when catalysts such as sulfuric acid are used with the same re actants. Thus, when benzene and 1,3-butadiene are reacted in the presence of sulfuric acid it has been reported that the product is diphenylbutane ' and that no phenylbutene is produced. _ In order to favor the desired ‘primary reaction I prefer to use moderate reaction temperatures, relatively short reaction periods, .and relatively high molar ratios of aromatic compoundto diole ?n reactant. The reaction maybe satisfactorily and conveniently conducted ata temperature -be-' peraturei's maintained below 150° F._, and prefer-‘ ablyabove-75" F., untilthe water is saturated tween about '70 and about 150° F., with a tem usingv'boron tri?uoride~containing complexes it is 5 amount of catalyst present should not exceed that perature between about'SO to 90° F. and about v1.10 ' to 120° F. being preferred; Temperatures above and boron ?uoride passes through'unabsorbed. 150° F., or below 70° F;, arejnot ‘tob'e. excluded, At this point a water-boroni?uoride mol ratio of approximately 1:1 is ordinarily obtained. The 45 however. The. average'reaction ‘time may be be tween a few minutes and a few hours, with satis-. catalyst may be, used in this form, or water may factory results being obtained with a reaction time be added until a desired higher mo'l ratio is .ob-‘ between about 5 and about 20 minutes. “The molar tained; alternately, the addition of boron fluoride ratio of aromatic compounds to diole?n in the feed may be halted at the desired hydrate concentraé tion by determination of the increase in weight 60 to a continuous reaction :step may be between about 2:1 and about lozlwith satisfactory opera or speci?c gravity of the liquid. Preferably, the tion generally being obtained with aratio between alkenylation catalyst of this invention comprises about 47:1 and about 6: 1. vIntimate mixing of the a hydrated boron fluoride containing from about reaction mixture, accompanied. by recirculation, 1.0 to about 1.5 mole of water per mol of- :boron ?uoride; This catalyst preparation reaction may 55 will generally result in higher effective ratios. in the reaction .zone.- In some instances it is- desir be ‘conducted, if desired, under pressure, partic able to use moderate superatmospheric pressures, ' ularly when using boron trifluoride or boron tri particularly with the lower boiling reactants, but chloride. ‘When an active catalyst of this inven-‘ generally the pressure need not be appreciably tion ‘loses appreciable quantities of‘ boron tri above that which will insure that the reactants ?uoride or other boron trihalide during use, its 60 are present in liquid phase and to insure that the activity decreases and‘for this reason it is desir catalyst is adequately saturated with the boron able to add during a continuous process small trihalide. As previously stated it is preferred that amounts’of boron trihalide initially used to pre the reacting mixture and, the catalyst be in fpare the catalyst, continuously or intermittently, timatelyadmixed. This may be accomplished by in order that the activity of the catalyst will .re-; efficient stirring mechanism, by continuously re main or be maintained substantially constant. In circulating in a closed cycle a substantial amount most instances the resulting active‘catalytic ma of the reaction mixture comprising. reactants, teriiall is a liquid and can be readily employed as products and catalyst, by pumping such. a re such, preferably with intimate mixing with the action mixture through a long tube .coil at. a rate reaction mixture. If ity is "desired to use such a such that conditions of turbulent ?ow exist, or by catalyst vin the solid form it may beiused' in ad, other means well known to those skllledin the m'ixture with porous granular catalyst'supports art of hydrocarbon alkylations. It is preferred such as activated charcoal, activated alumina, that the reaction mixture contain at least about 5 . activated bauxite, and the like, although when 5 per cent by volume off-the catalyst and that. the 2,404,120. 5 which will permit a continuous phase of reacting materials when the reaction mixture is intimately admixed. Thus it is desired that the. catalyst phase not be the continuous phase when a liquid catalyst is used. Inert materials may be present during the reaction, such ‘as relatively nonre active impurities normally accompanying the re actants, added low-boiling, para?in hydrocarbons ‘ thatlspeci?c limitations expressed in such ex amples-are not ‘to be. used to restrict my inven tion unduly. v ‘ ‘I ~ ‘g 1‘ w l . Example I i of ‘catalyst of composition comprising , 1.5 mols ‘of water to one mol of boron ?uoride was‘suspended in 312 grams of benzene by agi tation. Butadiene was introduced at a ?ow rate such as a parai?nic naphtha fraction,or“the like.‘ When 1,3-butadiene is the diolefi'n- reactant 10 of 15 grams per houruntill50 grams had been absorbed. The reaction was carried out at 89 to the monoalkenyl product is substantially com 95° F. The alkylate was processed as‘ above pletely the normal alkenyl derivative. 'With di-i and the benzene-free alkylate was fractionated ole?n reactants containing [a liigherinumber 'of to yield 300 grams (85% yield) of phenyl-butenes carbon atoms per molecule-‘suchhighi'yields" of the normal derivative will often notbe obtained 15 boiling between 356 to ‘365° F. (uncorr.). but it will still be possible to obtain quite sub; Example II stantial yields of the normal alkenyl derivative. In any case a fraction’ containing, or "comprising Operating under conditions similar to those given in Example I, toluene may be reacted with essentially, the desired normal alkenyl deriva tive may be readily separated from the reaction 20 piperylene (1,3-pentadiene) to produce n pentenyltoluene. In this instance, the toluene eiliuents, generally by passing the effluents to a free product is subjected to a preliminary frac settling chamber wherein the catalyst separates from a liquid phase containing unreacted charge tionation under 10 mm. pressure to ‘effect a rough separation of higher-boiling products stock and reaction products, and separating from this liquid phase, as by fractional distilla 25 from the pentenyltoluene. Final puri?cation involves fractional distillation at atmospheric tion, a fraction of any desired purity.‘ ‘ ~ pressure to give a product boiling at about As will be appreciated the normal alkenyl de 430-440° F. amouning to about 60 per cent of rivative may, in many instances, be a desired the total alkenylate. Analytical data and oxida product of the process. However, I have found that this material may be readily converted to 30 tion reactions indicate this materialto be essen tially 1 - (p-tolyl)-2-pentene. Nondestructive the normal alkyl derivative by nondestructive hydrogenation results in quantitative reductions hydrogenation. This hydrogenation will most to 1emethyl-4rn-pentylbenzene having substan often be conducted. in a manner such that the tially the same boiling range as the original alkenyl group is saturated by hydrogen. How ever, it will be appreciated that, particularly 35 alkenyl derivative. Although I have described my invention in when aromatic hydrocarbons are reacted in ac cordance with my invention, not only may nor considerable detail, with the inclusion of cer mal alkyl derivatives thereof be produced by such tain speci?c embodiments, it is not intended that a nondestructive hydrogenation, but the hydro genation may be extended to include partial or complete saturation of the aromatic nucleus. Thus it is possible to react a benzene with a low boiling 1,3-diole?n to produce a normal alkenyl derivative of said benzene, ‘and subsequently to the scope of the invention be limited unduly by ' such details. ' I claim: 1. A process for the production of normal ali phatic derivatives of aromatic compounds, which comprises reacting an aromatic compound with’ hydrogenate this product, in one or more steps, 45 a normal 1,3-diole?n in the presence of a com to produce a normal alkyl derivative or a corre plex catalyst resulting from substantially satu sponding normal alkyl cyclohexane. a naphthalene may be converted to a normal rating water with a boron trihalide. 2. A process for the production of normal alkenyl derivative, and this product may sub alkyl derivatives of aromatic compounds, which Likewise, , sequently be hydrogenated, in one or more steps, 50 comprises reacting an aromatic compound with to produce a normal alkyl derivative, a normal alkyl tetralin, or a normal alkyl decalin. For -a normal 1,3-diole?n in the presence of a com plex catalyst resulting from substantially satu such hydrogenations any suitable known nonde rating Water with a boron trihalide to form .a structive hydrogenation catalyst may be em normal alkenyl derivative of said aromatic com- I ployed which is capable of effecting saturation of the alkenyl group without saturation of the pound, separating from e?luents of said alkenyla tion a fraction comprising said normal alkenyl derivative, and subjecting said fractionto non destructive hydrogenation to form a normal al kyl derivative of said aromatic compound. aromatic nucleus or without reaction of any other reactive group in the alkenyl compound. So-called “Raney nickel” has been found desir3.-A process for the alkenylation of ‘an aro able in accomplishing this result when the hy matic hydrocarbon, which comprises reacting a drogenation is conducted at moderate tempera tures and pressures. More drastic hydrogena ' low-boiling normal 1,3-diolefin hydrocarbon with a molar excess of an alkenylatable aromatic-hy tion conditions will be necessary in order to pro duce the more saturated products just discussed. drocarbon under alkenylation conditions in the Thus, in the selective hydrogenation of the 65 presence of a catalyst resulting from saturating water with boron tri?uoride. . ~ ole?nic linkage, the rate of absorption of hy drogen may amount to about 1 mol per hour at 4. The process of claim 3 wherein said diole?n is 1,3-pentadiene. ' , ., pressures of 20 to 50 pounds per square inch and temperatures ranging from about '75 to about 5. The process of claim 3 Whereinsaid are-' 150° F. Nuclear hydrogenation can be effected. 70 matic hydrocarbon is naphthalene" and said di with the same catalyst at pressures of about ole?n is 1,3-butadiene. 500 to 5000 pounds per square inch and at tem-' 6. A process for the production of a normal. alkyl benzene, which comprises reacting a mix peratures of about 250 to 350° F. V - The following examples illustrate my inven tion further. However, it is to be understood . ' ture comprising a low-boiling normal 1,3-dio1e?n and a molar excess of benzene under alkenyla ' 2,404,120; 7. sulting from saturating water" with‘ boron‘ trie 1;3-diole?n*at a reaction temperature between ?uoride to produce a normal monoalkenyl deriva 'tive of benzene, separating from e?iuents of said alkenylation a fraction comprising said normal ; monoalkenyl derivative, and subjecting said _frac about '70and about 150° F. and under a‘ pressure su?icient to maintain the reactants in the liquid phase, said aromatic hydrocarbon and said di ole?n' being in a ratio of about 2:1 to 10:1 of tion to nondestructive hydrogenation under co'n- - aromatic hydrocarbon to diole?n, in the presence of a catalyst comprising a liquid complex result ditionssuch that substantially only said alkenyl group is saturated with hydrogen. I I _ 8 alkenyl'aromatic hydrocarbon, which comprises reactinga'naromatic hydrocarbon with a normal ' , 'tion conditions in the presenceof a catalyst'rei v ing from saturating water with boron tri?uoride, ' 7. The process of claim ?wherein said. diole?n and‘ maintaining a reaction time between about is 1,3-butadiene and normal butylbenzene is, pro. 5 and to about 20 minutes.’ duced. . v ' V ' g 8. Theprocess of claim 6 wherein said diole?n is 1,3-pentadiene and normal'pentylbenzene is, produced. 7 9.'A process for the production of an aryl butene, which comprises reacting an alkenylat able; aromatic hydrocarbon'with 1,3-butadiene at _ 12._ A process for the ‘production of a normal alkyl'aromatic. hydrocarbon, which comprises re 15 acting arr-aromatic hydrocarbon with a normal 1,3-diole?n at a- reaction temperature between about 70 and, about 150° F. and under a pressure suf?cient to maintain thereactants in the liquid phase, said aromatic hydrocarbon and said di a reaction temperature not greater than about 120° F., and with a substantial molar excess of 20 ole?n being in a ratio'of about 2:1 to 10:1 of aromatic hydrocarbon to diole?n', in the presence said aromatic hydrocarbon, in the presence, as of a catalyst comprising a liquid'complex result a’ catalyst, of a complex resulting from reacting ing from saturating water with boron tri?uoride; boron ?uoride with about 1 to about 1.5 molar maintaining a reaction time between about 5 and equivalents of-water. ’ ' ' j raboutl20'minutes whereby to form an alkenyl 10. A process for the alkenylation of an arc; ‘ matic hydrocarbon, which comprises reacting'a ' low-boiling-normal 1,3-diole?n hydrocarbon with aromatic hydrocarbon; and non-destructively hy drogenating ‘said alkenyl aromatic hydrocarbon to a normal alkyl‘aromatic hydrocarbon in‘ the a molar excess of an alkenylatable aromatic hyé presence of a nickel hydrogenation catalyst at a drocarbon at a temperature of about '70 to about 150? F. and under sufficient- pressure to maintain 30 pressure ‘of about 20‘ to about 50 pounds’ per - the reactants in the liquid phase in the presence of a- catalyst resulting from saturating Water with boron tri?uoride. ' } '11.'A process for the production‘ of normal . square inch and a temperature between about 75 and about 150°-F. ' ~ ' WILLIAM N. AXE.