US2072061A - Production of alkyl substituted aryl hydrocarbons - Google Patents

Description

:25 carbon material of the desired carbon content or P hydrocarbon m i is first chiorinatcd 25 to'i catalyze the splitting of the monochlorides j 55 the chlorides preparatory to the subsequent step conclusion'cf the condensation reaction, com- 55 I Patented F b, 2%), 1937- 7 2,072,06L

' UNITED STATES PATENT OFFICE PRODUCTION or 2mm suns'r'n'cm ARYL HYDBOCARBONS Charles A} Thomas, Wayne, Pa., asslgnorto The 'Sharples Solvents Corporation, Philadelphia,- Pa., a. corporation of Delaware 4 No" Drawing. Application August 28,1933, Serial No. 687,245

o 4 Claims. (or. 260-168) I The present invention relates tothealkylation' "in which the chlorides are condensedwith the I of aryl hydrocarbonsby. the substitution of alkyl aryl y 08 radicals of relativelyhigh carbon content for The higher molecular'weight chlorides whichnuclear hydrogen of such hydrocarbons.- It is are to be used in the condensation reaction arei re'particularly concerned with the production o close n boiling a ce. to the hydr c n of alkyl substituted aryl hydrocarbons having immw i h y, a d i d a t ey can on from eight to thirty carbon atoms in the alkyl be separated from the unr acted hydrocarbonsside chain. It is the object oi the invention'to with great ty-"f In some instances 01 0 110- p i produce compounds of this ty e by a commerrination or mixtures of isom ric par -fin y cially feasible process afiording a high yield oi; a o s t es a es actually ve each other, 10 thejiesired compound by arelatively inexpensive andin u hnsta m a 'a fl 18 3' procedure. Important economies are attained in tremely difiicult. ,A fu h r id fii ulty is ncoune- I the performance of the process by reason 01 th d y r on'cfthe fact t h large P 0P0 fact-that it mayb performed i r lati l i tion 01' thesealkyl chlorides are decomposed when pensive apparatus apdzbecause' the unused prody are e d'i l a n a Attempts 15 nets are recovered in aform which makes'possiat distillationcin such appar tus c rd ngly e ble their reuse in a repetition of theprocess; 1 $1111; n d sired splitting of, much of the chlo- I Theprocess of-the invention is based iundaa e ma ial 'to P e cleflns d ydro-- mentally upon'the well-known Friedel and Crafts l ic i rn c d cv littin in such Y reaction by which alkyl chlorides are condensed, an opera mit is necessary that the distilla 20 y with substituted or unsubstituted aryl hydrocare nducted in apparatusma'de of glass or other Lions in the presence of anhydrous aiuminun expensive ne t material which does not ct a chloride or other equivalent catalyst. 3 It involves a 8 f a-lystto Cause h splitting 0! F 8 c oriaesthe initial .step of chlorinating parafiin hydron he practice of the pr nt invention range 1 and the. condensation of chlorinated hy- 9 Produce m x re of hydrocarbons and chlodrocarbon material with an aryl compound in the ag -"E g c i a ici i f t y fil n esenceof, a catal st. Y P Orme 3 P 11g gaseous c 0113116" ji number of diific ulties are encountered inc-om; 8 ui o f fl n h s chlorinanection with attempts to perform such-:a series; j i c cn is i continued long' before com-- .39

of operations in the production otsalkyl chlorides him-"191011 Of a cula ch 9 0 9 r of high molecular weight and the subsequent sep- W h e yd ocarbon under treatment. This 1 aratlon ojf'mono-chlorides so .formed h'om-unkgl s fh l a h fi 5 22 31 1 i ilgl 'gg reacted paraflin hydrocarbons and poly-chlorides. 0 8 5S 9 i 0 ma The performance of the chlorination operation 'fl that. dBc0mR0$itih Oi q f d 35 by a procedure involving the conversion '01 the E e leactmni a subsequent l/' r i 01 Poly" major portion of the h drocarbon into chlorides 2333 31 n z g s zfi g ig g cg giei fis necessarily resultsv in e production or a large v Y proportion of undesired poly-chlorides. Even'in production of any 43 P casesgin which chlorination is terminated long beqc s v {ore amolecular proportiohIQf chlorine has com= fia 538? 2;2 22

bined-with'the hyqmcarbon'agreat deal of entire mixed-ch l rides and h a'r:flin y desired formation of polychloride material ocdmcrbbns is mi 7 1 I xed -W1th the aryl hydrocarbon is??? when the react a 'with whichit is to'becpndensed. rt'isitobe- 45 apparatus. apparatus tending noted that no attempt at separation of r I formed to produce oleflns and hydrochloric acid,.. gg gggzitgggm gf g ggag fii V as olefins so formed have atendency to promptly A alkyljhydmcarbons and alkyljmondes is next i, m with more m P Pmduce undesired stlrred during the addition of a. suflicient quantity 5o dichlorides. If the chlorination operation isnot oiranhydmus aluminum chlonge or other-equlwp n carriedto substantial-completion, seri u F 9 1 'lent catalyst to effect condensationofthe alkyl' lems 0t distillatiom are also encouhtered in sepachlorides with th hiy]; hydrocarbon m m-E1. raiicn un acted pa aflin hydro arbons .from sinc with the Friedeiandcrafts reaction. .At the w plex is decomposed with dilute hydrochloric acid or cold water and the mixture distilled until the unused hydrocarbon is recovered, and further distilled to effect separation of the desired alkyl substituted aryl hydrocarbon from the residue.

In a typical example of the practice of the invention, the following procedure was adopted:

1000 grams of mixed parafiin hydrocarbon material consisting principally of dodecane was partially chlorinated by bubbling chlorine through the material until it had gained 70 grams in weight; i. e., until approximately 35% of the hydrocarbons had been converted to monochlorides. 3 liters of benzene were added to the mixture of chlorides and paraffin hydrocarbons and the mixture was stirred during the addition of 200 grams of anhydrous aluminum chloride. After one-half hour the complex was decomposed by the addition of a small amount of dilute hydrochloric acid and the mixture was steam distilled until all of the unused benzene had been recovered. The residue was then vacuum distilled and yielded 660 grams of hydrocarbon material.

Tests with bromine water indicated that this hydrocarbon was saturated and could hence be used in. a second chlorination and condensation in connection with a repetition of the process.-

238 grams of material having a boiling range .from 185-210 C. at 25 mm. pressure and consisting principally of lauryl benzene was recovered. A residue of 98 grams which is believed to have comprised principally dilauryl benzene, was obtained.

It Will be noted that the practice of the inven-- tion in accordance with the above described procedure involves avoidance of the; loss of valuable paraffin hydrocarbon and other difficulties incident to the formation of dichlorides such as would be encountered in connection with attempts to effect more complete chlorination of the hydrocarbon mixture or chlorination in metal apparatus and that the use of the entire mixture of chlorides and paraflin hydrocarbons in the subsequent step of condensation with the aryl hydrocarbon obviates the diificult problems of fractionation referred to above. While great difficulty would be encountered in attempts to Sep arate the unreacted paraflin hydrocarbon material from corresponding chlorides, the separation of this material from the alkyl substituted aryl compounds by distillation is not difiicult, as these last-mentioned compounds have boiling ranges much higher than the parafllns or chlorides used in the condensation reaction.

Modifications will be obvious to those skilled in the art and I do not therefore wish to be limited except by 11319 590138 of my subioined' claims. The chlorination may, for example, be carried out in the vaporphase provided a substantial molecular excess of hydrocarbon is used. In the interpreta tion of the claims, I wish it to be understood that the term aryl compound is intended to include not only unsubstituted aryl hydrocarbons, such' alkyl poly-chlorides, mixing the mixed mass of alkyl chloride and paraflin hydrocarbon with the aryl compound which is to form the aryl radical of the desired derivative, condensing the alkyl chloride of the mixture with the aryl compound and thereafter separating the uncondensed material from thedesired derivative by distillation to obtain amass of the desired alkyl derivative substantially free of paraflin hydrocarbon and chicrine derivatives.

2. The method of producing a mass ofv material comprising essentially a mono allgvl derivative of an aryl compound containing from eight to twenty carbon atoms in its alkyl radical which comprises chlorinating paraflin hydrocarbon material corresponding in carbon content to the alkyl radical of the desired derivative to an extent sufficient to produce a mixture of the paraflin hydrocarbon and the corresponding alkyl monochloride but insufficient to produce any substantial quantity of alkyl polychlorides, mixing the mixed mass of alkyl chloride and parafiin hydrocarbon with the aryl compound which is to form the aryl radical rine derivatives.

3. The method of producing a mass of material comprisin'g essentially a mono-alkyl derivative of an aryl compound which comprises chlorinating paraflin hydrocarbon material corresponding in carbon content to the alkyl radical of the desired derivative to an extent suflicient to convert a part but less than one-half of the material into the corresponding alkyl mono-chloride while avoiding production of any substantial quantity of alkyl polychlorides, mixing the resulting chloride together with the unreacted hydrocarbon with the aryl compound which is to form the aryl radical of the desired derivative, condensing the alkyl chloride of the mixture with the aryl compound and thereafter separating the uncondensed material from the desired derivative by distillation to obtain a mass of the desired alkyl derivative substantially free of paraffin the corresponding alkyl mono-chloride but not sufficient to produce any substantial quantity of alkyl poly-chlorides, mixing the resulting mass of alkyl chloride and parafiin hydrocarbon with the aryl compound which is to form the aryl radical of the desired derivative, condensing the alkyl chloride of the mixture with the aryl compound and thereafter separating the uncondensed matedial from the desired derivative by distillation to obtain a mass of the desired alkyl derivative substantially free of paraflin hydrocarbon and chlorine derivatives, said process being carried out while maintaining the reactants out of contact with materials, such as various metals, that cause the formation of undesirable compounds.

cmmrns A. THOMAS.