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d grates .iiatent @tiice 1 F. Patented May 21, 1963 1 2 3,999,819 In addition, these prior metalation processes are gen erally deemed unsuitable for commercialization due to the dif?culties and 'high costs connected with their use. TRANSMETALATKUN PROCEEéS Walter E. Foster, Baton Rouge, La, assignor to Ethyl Corporation, New York, N.Y., a corporation of Virginia N0 Drawing. Filed Feb. 24, 1959, Ser. No. 794,817 12 Claims. (Cl. 269-665) This invention relates to ‘a method of preparing organic compounds and more particularly to the preparation of aliphatic polyole?n hydrocarbons and organo alkali metal compounds. Further, the prior processes require many separate proc ess steps as well as long periods for appreciable reaction which at best converts only half of the reactants, e.~g., toluene ‘and sodium, to the desired product and com pletely degrades the chlorine values to sodium chloride. The above objectionable features of the prior art mate rialiy increase the overall costs of the desired end prod uct, and make its manufacture by these processes com mercially unattractive. Aliphatic polyole?n hydrocarbons are extremely inter It is accordingly an object of the present invention to esting chemical compounds which are readily converted provide a process for the manufacture of aliphatic poly into valuable industrial materials by processes well known 15 ole?n hydrocarbons. Another object is to provide a proc to those skilled in the ‘art. Of particular interest are ess of the above type which is suitable for manufacturing those long chain aliphatic polyole?n compotmds Where a very wide variety of aliphatic polyole?n hydrocarbons, in the unsaturation is located near the terminal carbons of the molecular chain. These compounds can easily be processed to form long chain (4 or more carbons) polycarboxylic ‘acids, esters, polyglycols, polyaldehydes, polyketones, polyacetals, polyethers and other polyfunc including many which were heretofore unknown or not capable of preparation by prior methods. Still another object of this invention is to provide for the conjoint manufacture of an aliphatic polyole?n hydrocarbon and a metalated organic compound. Another object is to tional compounds which are of great industrial value. provide a process of the above character which can be For example, octa-2,6-diene can be oxidized easily to form conducted over a relatively broad temperature range. An succinic acid. Or, if desired, the octadiene can be treated 25 other object is to provide a simpler, more economical chemically to form the heretofore unavailable 2,3,6] process of the above type. Other objects and advantages octatetrol. Heretofore, there has been no known method of the invention will be apparent from the following for manufacturing many other similar compounds and the description and appended claims. manufacture of numerous known compounds of this type It has now been found that a wide variety of valuable has been limited to the use of di?icult and expensive 30 aliphatic polyo-le?n hydrocarbons and organo alkali metal processes, thereby increasing their cost and limiting their compounds, which in some cases were previously un commercial utilization. known, can be simultaneously prepared by reacting an The transmetalation of aryl compounds is ‘a well known organic compound, particularly one having an active hy chemical process which can be employed to convert rela drogen, with an alkali metal aliphatic polyole?n com tively inexpensive and available hydrocarbons into valu 35 pound. Both of these valuable co-product-s have par ticular utility as intermediates in the production of a able derivatives, i.e., carboxylic acids and their esters, polycarboxylic acids and their esters, alcohols, etc. Typi very wide variety of commercial chemicals and some cal examples are the formation of phenylacetic acid or heretofore unavailable chemicals, particularly, certain phenylmalonic acid and their derivatives from toluene mono and polycarboxylic acids, esters, alcohols, aldehydes, and the formation of phenylenediacetic acid from Xylene. 40 nitriles, etc. These conversion processes are not used presently be cause of the many disadvantages inherent in their opera tion. Thus, prior metalation reactions [Industrial and En_ gineering Chemistry 46 No. 3, page 539 (1954)] were conducted by ?rst chlorinating an aromatic compound, such as benzene or toluene, to produce the corresponding chloroaromatic compound i.e. chlorobenzene or chloro toluene. The chloroaromatic compound was then re acted with sodium or ‘another alkali metal to form the More particularly, the process of this invention can be conducted by initially contacting an organic com pound containing an active hydrogen, such as aryl, acetylenic, nitrile, aliphatic carboxylic acid salt or cyclo dienyl compounds, with an alkali metal aliphatic polyole ?n compound, e.g., disodio octadiene, at a temperature not greater than about 40° C. in the presence of an ac tive solvent. If desired, the reaction can be completed at a temperature below about 40° C. However, in a pre aromatic alkali metal compound, i.e., phenylsodium. The 50 ferred embodiment of this invention, following the initial low temperature contact period, substantially all of the so~formed aromatic alkali metal compound can then be reacted with substances containing reactive groups, such as carbon dioxide, sulfur dioxide, nitriles, alkyl halides, active solvent is removed at a temperature below about 40° C. and the reaction is completed at an elevated tem perature in the range between about 50° C. and 250° C. aromatic nitro compounds, acid anhydrides and com pounds containing reactive hydrogen atoms which are able 55 As a variation in the process, the transmetalation re‘ to be replaced by an alkali metal. For example, reacting action noted above can be conducted simultaneously with phenylsodium with toluene and carbonating the product the formation of the alkali metal aliphatic polyole?n. In so-formed, results in the formation of the sodium salt one such method, an active solvent and an alkali metal of phenylacetic acid which can be hydrolyzed, if desired, dispersion are added to a reactor equipped with a stirrer to the free acid. Alternatively, aliphatic halides were re 60 and re?ux condenser. The alkali metal can be dispersed acted with sodium and the so-formed alkyl sodium com in an inert solvent, such as isooctane, or, if desired, in pounds were heated with ‘aromatic compounds to form the organic compound to be trausmetalated in the process. the desired aromatic alkali metal compounds by trans An aliphatic conjugated polyole?n is then added with metalation. agitation as a dilute feed stream (usually as a dilute gas 65 These prior metalation processes, however, give as a by stream) over a period of time to form initially the alkali product equal molar quantities of (l) the hydrocarbon metal aliphatic polyole?n, preferably the dimetalated which was chlorinated in the ?rst reaction of the process derivative. The organic compound to be transmetalated and (2) the desired metalated product. The process, therefore, requires preparation of the desired product from can be added to the reaction either in whole or in part, before or during the addition of the conjugated poly one half can be recovered as a valuable material. and/or as a diluent for the active solvent. The reaction large quantities of the ‘starting material and requires 70 ole?n. In some cases, the organic compound can be employed as the dispersing medium for the alkali metal handling large quantities of materials, of which only about 3,090,819 4 3 For example, octa-1,6-diene ‘can be reacted with an oxi dizing agent, such as cold potassium permanganate to form 1,2,6,7 octanetetrol. Further, octa-1,6-diene can be reacted with a halogen to produce the corresponding polyhalide or contacted with carbon monoxide and hydro gen under certain process conditions to produce Z-methyl azelaic dialdehyde which can then be oxidized to Z-methyl then proceeds for a period of time with rapid stirring until complete. In the preferred embodiment of this invention, substantially all of the active solvent is re moved at a temperature below 40° C. following the addition of at least a part of the organic compound to the reactor containing the alkali metal aliphatic poly ole?n compound and the active solvent. The reaction temperature is then raised to between about 50° and 250° C. in order to complete the transmetalation reaction. azelaic acid. Similarly, otherpolyfunctional compounds without prior separations. These subsequent chemical acid, 3-phenyl pimelic acid, 3,4-diphenyl adipic acid, 4,5 reactions can be conducted in the reaction mixture in which the organo alkali metal compounds were formed, diphenyl suberic acid and other similar alcohols, alde hydes and acids. Some typical examples of halogenated materials which can be prepared from the aliphatic polyole?ns obtained' in this invention are 2,3,6,7 tetrachlorooctane, 1,2,6,7 can be prepared by subjecting the polyole?ns to other The aliphatic polyole?n hydrocarbon and the organo al 10 well known reactions and further reacting, the’ products so-formed. Typical examples of other such polyfunc kali metal compound formed by this reaction can there tional compounds formed from the polyole?n products after ‘be separately recovered. If desired, these materials of the present invention are 2,3,6,7-octanetetrol, 1,2,7,8 can be further reacted chemically to convert them'into octanetetrol, 2,7-octanediol, adipic acid, Z-methylglutarie, other valuable materials. Since the organo alkali metal compounds, formed by this process tend to be unstable 15 acid, 1,2-dimethyl glutaric acid, 2,5-dimethyl adipic acid, , 2,3,6,7-tetramethyl suberic acid, 3,4-dimethyl pimelic and di?icult to handle when exposed to air, it is frequent acid, 4,5-dimethyl suberic acid, 2,3,4,5-tetramethyl adipic ly desirable to subject them to further chemical reactions thereby forming other valuable materials whose physical and chemical properties are such as to facilitate their separation from the reaction mixture. For example, the organo alkali metal compound can be reacted in typical tetrachlorooctane, 3,4,7,8 tetrachlorodecane, 2,3,6,7 tetra Grignard type reactions with carbon dioxide to give car 25 chloro-4,5 dimethyloctane, 2,3,6,7 tetrachloro-2,3,6,7 tetramethyloctane, 2,3,6,7 tetrach1oro-1,4,5,8 tetraph'enyl boxylicacids, with sulfur dioxide to give sul?nic acids, with formaldehyde, epoxides or oxygen to give alcohols, with cyanogen chloride to give nitriles or used generally as a Grignard type reagent in reactions with esters, acid anhydn'des, aldehydes, ketones, halides and nitriles. 'I‘he 30 duces organo alkali metal compounds as valuable co aliphatic polyole?n hydrocarbons formed in this reaction products of the above-mentioned aliphatic polyole?n octane, the corresponding bromo and iodo compounds and=the like. As described above, the present invention also pro-7 hydrocarbons. In general, alkali metal substitution com pounds of an organic compound having an active hydro and the like. ' gen, particularly aryl, acetylenic, nitrile aliphatic car \A wide variety of aliphatic polyole?n hydrocarbons can be produced by the present invention. Typical examples 35 boxylic acid salt and cyclodienyl compounds or the mono or polysubstituted derivatives of aryl compounds, can be of such hydrocarbons are the octadienes, such as octa can be converted to aldehydes, alcohols, carboxylic acids 1,6-diene, octa-l,7-diene and octa-2,6—diene; the substi prepared by the process of this invention. These aryl tuted octadienes, such as 4,5 dimethylocta1,6-diene, 4,5 derivatives, however, should not contain any functional, groups such as the hydroxy, carboxyl, nitro, halide (other than ?uoride) and the like groups which are reactive towards alkali metals. Aryl compounds which are suit able for forming alkali metal substitution compounds in dimethylocta-2,6-diene, 2,7 dimethylocta-1,6-diene, 2,7 dimethylocta-2,6-diene, 2,7 dimethylocta-1,7~diene, 3,6 di methylocta-1,6-diene, 3,6 dimethylocta-2,6-diene, 3,6 di methylocta-3,6-diene, 2,6 dimethylocta-lJ-diene, 2,6 di methylocta-2,6-diene, 3,7 dimethylocta-1,6-diene, 2,3,6,7 tetramethylocta - 1,6 - diene, 2,3,6,7 tetramethylocta-1,7 diene, 2,3,6,7 tetramethylocta—2,6-diene 2,3,6,7-tetra-t butylocta-1,6-diene, 2,3,6,7 - tetra - t - butylocta-1,7-diene, 2,3,6,7-tetra-t-butylocta-2,6-diene, diene, 1,8 diphenylocta-2,6—diene, diene, 1,5 diphenylocta-2,6-diene, diene, 1,5 diphenylocta-l,7-diene, diene, 4,5 diphenylocta-1,6-diene, 1,8 1,8 1,5 4,5 4,5 dipheny1octa—1,6 diphenylocta-l,7 diphenylocta-1,6 diphenylocta-2,6 diphenylocta-l,7~ diene, 1,4,5,8 tetraphenylocta-1,6-diene, 1,4,5,8 tetra phenylocta—1,7-die-ne, , 1,4,5,8 tetraphenylocta-2,6‘diene, 45 clude benzene, diphenyl methane, triphenylmethane, phenylacetylene, acenaphthene, retene, indene, aryl ethers as, for example, anisole, aryl carboxylic acid salts, aryl sulfonic acid salts, aryl ?uorides, furan, ?uorene, thio phene, pyr-role, pyrazole, imidazole, triazoles, tetrazoles, oxazole, thionaphthene, indole, couman'n, quinoline, cin noline, naphthyrid-ine, carbazole, thioanthrene, racridine, 50 phenazine ‘and the mono and poly-alkyl derivatives of these aryl compounds. Other organic compounds which can be metalated in this improved process are acetylene and homologues of acetylene, acetonitr-ile and its homologues, cyclopenta 1,6-diene, 2,3,6,7 tetraphenylocta-l,7—diene, and the like. 55 diene, Z-methylcyclopentadiene, 3-methy1cyclopentadiene, 2,3-dimethylcyclopentadiene, l-methylcyclopentadiene, 3. Other typical examples of the type of aliphatic polyole?n 2,3,6,7 tetraphenylocta-2,6-diene, 72,3,6,7 tetraphenylocta hydrocarbons formed by the present invention are 4~ methylnona-2,6-diene, 4-methylnona-l,6-diene, deca—2,7 diene, deca-2,8-diene, deca-3,7-diene, 5,6 dimethyldeca 2,8-diene, 5,6 dimethyldeca-2,7-diene, 5,6 dimethyldeca 3,7-diene, 3,4,5,6,7,8 hexamethyldeca-2,7-diene, 3,4,5,6,7,8 hexamethyldeca-2,8-diene, 3,4,5,6,7,8 hexamethyldeca 3,7-diene, dodeca-2,4,8,10-tetrene, dodeca-l,3,9,1l-tetrene, dodeca-2,4,9,l1-tetrene, 4 ethenedeca-1,6,8-triene, 4,5 di etheneocta-1,7-diene, 4 ethenedeca-l,5,7,9-tetrene and other polyole?ns belonging to the group having a gen eral formula of CnH2n_2 which heretofore have been either extremely di?icult and costly to prepare or which are unknown at the present time. ;Ehylcyclopentadiene, 3-propylcyclopentadiene land the . e. The aliphatic carboxylic acid salts, suitable for use in 60 the process of this invention, are preferably alkali metal salts ‘and contain from 2 to 20 carbon atoms. Best re sults are obtained ‘with monocarboxylic acid salts. Typi cal examples of alkali metal aliphatic salts are sodium acetate, sodium propionate, sodium butyrate, sodium hex anoate, the corresponding lithium and potassium salts and other alkali metal salts containing up to 20 carbon atoms. Typical examples of transmetalated alkali metal com pounds which can be prepared by the process of this in The aliphatic polyole?n hydrocarbons prepared by the 70 vention are phenyl sodium, phenyl lithium, benzylsodium, benzyl potassium, diphenylmethyl sodium, o-anisylsodi um, p-rnethylbenzylsodium', xylylene disodium, pyrryl ‘ functional compounds such as polycarboxylic acids, poly sodium, a-naphthobenzyl sodium, sodium acetylide, po aldehydes, polyketones, polyacetals, polyethers, poly tassium acetylide, a-sodio acetonitrile, cyclopentadienyl alcohols, polyhalides, polynitriles, polyamides, polyesters, polyurethans, polynitro compounds, polyepoxides, etc. 75 sodium, cc-SOdlO sodium acetate, OL-POtBSSllII'l’l potassium ' present invention can be converted to long chain poly ‘spacers S 5 ‘acetate, OL-SOdlO sodium propionate, a-SOdiO sodium cap ‘roate, a-sodio sodium palmitate, a-lithio lithium stearate, a temperature above about 50° C. in order to complete etc. ployed with the higher boiling organic compounds and the reaction. In general, higher temperatures are em temperatures between about '50” .and 250° C. can be These alkali metal compounds can thereafter be further reacted to form other valuable materials, as for example, C11 satisfactorily employed, although temperatures between about 80° and 150° C. are preferred. phenylacetic acid, p-phenylene diacetic acid, terephthalic acid, .trimesic acid, and other aryl carboxylic acids. Further, these alkali metal compounds can be reacted with The reaction time required to complete the transmetala tion reaction, while not too critical, is an important factor in the present invention. Satisfactory yields of the ali formaldehyde to form primary alcohols, with other alde hydes to form secondary alcohols, ‘with ketones and 10 phatic polyole?n products are obtained only when the transmetalation reaction is allowed su?‘icient time to pro esters to form tertiary alochols, with nitriles to form ceed to completion. From the chemistry of the trans ketones and with halogenated compounds to undergo a metalation reaction, a transfer of two atoms of the alkali condensation reaction. metal per molecule of aliphatic polyolefln hydrocarbon The alkali metal aliphatic polycle?n compounds em ployed in the practice ‘of the present invention can be 15 formed is involved. it appears that an incomplete trans metalation reaction normally results in the formation of a prepared by a variety of processes. As pointed out monoalkali metal aliphatic polyole?n compound and a above, in one method of preparing these alkali metal decreased yield of the desired polyole?n hydrocarbon. aliphatic polyole?n compounds, a dilute stream of a This situation is particularly disadvantageous when the conjugated aliphatic polyene is permitted to react with ?nely dispersed alkali metal in the presence of an active 20 combined reaction product is to be further reacted, e.g., by a carbonation reaction. In such cases, not only does solvent. The alkali metal dispersion is generally pre the transmetalated compound react with the carbon di pared by rapidly stirring and then cooling a mixture of oxide :but any co~present monoalkali metal aliphatic poly the molten metal and an inert solvent containing from oleiin undergoes the same reaction to form a product con 1 to 50 percent, and preferably from 5 to 35 percent by weight of the metal, based on the total weight of the 25 sisting of the alkali metal salt of a complicated mixture dispersion, thereby solidifying the metal to form particles having a size generally less than about 50 microns, preferably less than about 10 microns. Dispersing known to the art, e.g., oleic acid, dilinoleic acid, quently can be used. The so-formed alkali metal persion, consisting principally of the metal dispersed within an inert solvent, is then mixed with the active solvent to be used in the polyole?n addition reaction. In some cases the reaction can be conducted’ in the presence of a polynuclear aromatic hydrocarbon, such as naph thalene .or terphenyl, as a catalyst. The reaction tem perature is maintained below 40° C. and usually below 0° C. of carboxylic acids. When practicing the preferred embodiment of the in and vention wherein the reaction is completed at a tempera aids ture above 50° C., it is desirable to contact the alkali fre dis 30 metal aliphatic polyole?n ‘with the other reactants for a The reaction proceeds smoothly as the conju reaction period of not less than about one half hour at a temperature below about 40° C. followed by a reaction period of not less than about one hour at a temperature above 50° C. In the event that it is desired to practice the low temperature embodiment of this invention, where in the transmetalation reaction occurs concurrently with the formation of the alkali metal polyole?n compound, it is generally desirable and frequently necessary to allow gated aliphatic polyole?n is added slowly and the alkali metal aliphatic polyole?n compound usually separates as the reaction to continue for at least an additional one half a solid phase. Still another method for preparing these polyole?n compound, particularly if this reaction period alkali metal compounds is by reacting the conjugated aliphatic polyole?n with dispersed alkali metal in the is less than about 7 hours. This additional reaction period is particularly desirable if the combined reaction products are to be subjected to a subsequent reaction, e.g., carbonation, sulfonation, etc. Pressure is not too ‘critical in the practice of this in presence of a mixture of an active solvent and the com pound containing an active hydrogen with which the alkali metal aliphatic polyole?n compound is to be re acted. By this method, the transmetalation reaction of the present invention can be carried out concurrently hour following the complete formation of the alkali metal vention. Pressures above atmospheric can be used if desired or when necessary to con?ne the solvents when with the formation of the alkali metal aliphatic polyole?n compound. In both methods, effective agitation of the reaction mixture is desirable. While it is usually preferred ‘to employ sodium or particularly when it is desired to remove the active sol vent prior to completing the reaction at an elevated tem potassium as the alkali ‘metal component of the organo perature. Generally, however, it is preferred to operate metallic compound used in the present invention, all of temperatures above their atmospheric boiling point are employed. Subatmospheric pressures can also be used, at atmospheric ressure primarily ‘as a matter of con the other alkali metals are suitable. Thus, lithium, 55 venience and ease of operation. rubidium, cesium and francium can be employed in the The active solvents suitable for use in the present in preparation of the alkali metal aliphatic polyole?n com vention can be selected from the group consisting of pounds with ‘equally good results. Mixtures or alloys of alkali and alkaline earth metals also may be used. The use of sodium is preferred, however, primarily be cause of cost and availability. Although the present invention can be carried out over a wide range of temperature, the initial reaction temper ature employed is of importance. Generally, satisfactory others, acetals and tertiary amines. A preferred group of others for use in the present in 60 vention include both aliphatic mono- and polyethers. The preferred monoethers have a CH3-O— group and have an oxygenzcarbon ratio not less than 1:4. Typical exam ples of these preferred monoethers are dimethyl ether, methyl ethyl ether, methyl isopropyl ether, methyl n results are obtained when temperatures up to about 40° C. 65 propyl ether or mixtures of these ethers. The above are maintained during the initial stages of the reaction although it has been found that reaction temperatures below about 0° C. are preferred and give the best re sults. Satisfactory results have also been obtained when operating at temperatures as low as —80° C. In the preferred embodiments of this invention where it is de sired to operate at higher temperatures after the initial reaction period, .the active solvent is removed at a tem others can also be mixed with hydrocarbon solvents, if desired. The preferred polyethers are ethylene ‘glycol diethers, such as methyl methyl, methyl ethyl, ethyl ethyl, methyl |butyl, ethyl butyl, butyl butyl, butyl lauryl; diethylene glycol others, such as methyl methyl, methyl ethyl, ethyl butyl and butyl lauryl; trimethylene glycol others, such as dimethyl, diethyl, methyl ethyl, etc; glycerol ether-s, such perature below about 40° C. and preferably below about 0° C. and the residual reaction mixture is then heated to 75 as trimethyl, dimethyl ethyl, diethyl methyl, etc.; and 3,090,819 7.. cyclic’ ethers, such as dioxane, tetrahydrofuran, methyl, glycerol formal, dimethylene pentaerythrite. was quenched with 100 parts of distilled water in apnitro-p gen atmosphere. The aqueous product solution was sep-, arated from the isooctane solution and acidi?ed with corn-p centrated hydrochloric acid to give .a white?occulent A wide variety of acetals can also be used in the pres ent invention. Typical examples of suitable acetals are methylal, 1,1-dimethoxy ethane, 1,1-dimethoxy propane, product containing the desired phenyl acetic acid. This, ~1,1-dimethoxy butane, methylal glycol formal, methyl product was distilled under reduced pressure to give 48.3 _ glycerol formal, etc. The preferred iacetals are methylal, parts of the phenylacetic acid, having a melting point of methylal glycol formal and methyl glycerol formal. 63° to 70° C. and a neutralization equivalent of 138. This corresponds to a yield of 71 percent, based on the invention including both aliphatic and aromatic amines. 10 butadiene reacted. This material was recrystallized to. The preferred tertiary amines for use in this invention produce a product having amelting point of 76-77,‘1 C. A wide variety of tertiary amines are suitable for tins are trimethyl amine, dimethyl ethyl amine, tetramethyl methylene diamine and N-methyl morpholine. The amount of active solvent employed in the reaction" mixture can ‘be varied considerably without departing 15 from the scope of the invention. The amounts used will EXAMPLE II This example illustrates the preferred embodiment of generally depend on the particular reactants and solvent used. The isooctane ‘fraction, above, yielded 16.8 parts of an isomeric mixture of octadienes with the octa-1,6-diene' isomer being present as the, predominant isomer. the process of this invention wherein the reaction is ini In general, the use of from 100 to 2,000 cc. of solvent per gram mole of alkali metal aliphatic polyole?n compound ibeing reacted is recommended as a suitable reaction dilution. When a diluent is used along with the active solvent, su?icient active solvent should be present tiated at a low temperature and completed at an elevated temperature. To the reactor of Example I were added 320 parts of dimethyl ether and 25 parts of sodium having anraverage particle size of about 10 microns and dispersed in an equal to have an active promoting effect upon the reaction. In the speci?c embodiment of the invention wherein the amount of toluene. Twenty-?ve parts of butadiene were transmetalation reaction occurs concurrently with the 25 added in a dilute gas stream over a period of 5 hours, dur formation of the alkali metal polyole?n, it is preferred to ing which time the reaction temperature was maintained use a reaction medium which contains a weight of active at —30° C. The reaction mixture was stirred for an ad! solvent at least as great as the weight of any co-present ditional % hour at —30° C. and 260 parts of dry toluene diluent. were added. The reaction mixture was warmed over a For those reactions in which it is desired to heat the 30 period of one half hour to remove most of the dimethyl reaction mixture during the ?nal stages of the transmetala ether solvent at a temperature below 20° C. and the last tion, it is generally preferred to use a more volatile active traces of the solvent were removed by heating the mixture ’ solvent so that it can be removed more conveniently. to 100° C. The mixture was then heated for 2 hours at The proportion of alkali metal aliphatic polyole?n compound to the organic compound having an active hy 100° to 105° C. with rapid stirring to prevent charring drogen varies. over a wide range depending on the com and then cooled to 0° C. The cooled mxture containingv benzyl sodium and an isomeric mixture of octadienes pounds employed and the degree of metalation desired. was poured on to an excess of crushed Dry Ice to convert ‘ In order to obtain ‘a satisfactory conversion of the alkali the benzyl sodium to sodium phenyl acetate. The excess Dry Ice was evaporated and the reaction mixture was 40 quenched with 100 parts of distilled water in a nitrogen sirable to use at least the required theoretical amount of atmosphere. The product was separated into an aqueous the organic compound to be transmetalated. Generally, : and organic phase. The aqueous phase was acidi?ed with when monometalation of the compound to be transmeta concentrated hydrochloric acid to give 50.7 parts of lated is desired, at least a stoichiometric amount of this phenylacetic acid, having a melting point of 63° to 770° C. compound is employed, and frequently it can be present and a neutralization equivalent of 138.‘ This corresponds in excess of this amount. Thus, as mentioned above, it to a yield of 80.5 percent based on the butadiene. The metal aliphatic polyole?n component to the correspond ing aliphatic polyole?n hydrocarbon, it is generally de often can be used conveniently as a reaction medium dilu ent or as the principal solvent in the latter stages of the organic phase yielded an isomeric mixture of octa-l,6-_‘ ‘diene, octa-1,7-diene and octa-2,6-diene with the octet-1,6 preferred embodiment of the transmetalation reaction wherein the active solvent is removed prior to bringing diene isomer largely predominating. the reaction to completion at an elevated temperature. 50 Where it is desired to polymetalate an organic compound, it is preferred to'employ substantially about stoichiometric quantities of each of the reactants, i.e., the alkali metal aliphatic polyole?n and the organic compound to be trans metalated. sults are obtained: Methyl ethyl ether Methyl isopropyl ether Ethylene glycol dimethyl ether 1,1-dimethoxy ethane Tetrahydrofuran ' The following non-limiting examples illustrate the process of the present invention. All proportions are given ‘by weight. ‘ EXAMPLE I A stirred reaction vessel was equipped with a con denser having a gas inlet tube reaching below the surface of the reaction mixture. About 250 parts of dimethyl ether and 17.2 parts of sodium dispersed in 60 parts of toluene were then added. Twenty-seven (27) parts of butadiene were gradually added in a dilute gas stream over a period of 5 hours while maintaining the reaction mix ture at a temperature of —30° C. The reaction mixture Was stirred for an additional hour at —-30° C., to com EXAMPLE III When any of the following active solvents are employed in the processes of Examples I and II, similarly good re 60 Dioxane Methyl glycol formal Trimethyl amine Methyl diethyl amine Tetramethyl methylene diamine EXAMPLE IV Example I is repeated except that p-xylene is metalated instead of toluene. In this example, 26 parts of p-xylene are employed instead of the 60 parts of toluene. Similar plete the conversion of toluene to benzyl sodium and 70 yields are obtained except that p-phenylene diacetic acid is obtained as a product instead of the phenyl acetic acid the formation of an isomeric mixture of octadienes. There of Example I. ' after, 290 parts of isooctane were added and the mixture EXAMPLE V was poured on to an excess of crushed Dry Ice to con vert the benzyl sodium to sodium phenyl actate. The The following runs are typical examples of the wide excess Dry Ice was evaporated and the reaction mixture 75 variety of aryl compounds which can be metalated by the T I p 3,090,819 9 16 present invention. The apparatus and method of Ex amples I and II are used except that the aryl component is varied. Similar results to those of Examples I and ample, 34 parts of cyclopentadiene are used. The yield of products obtained is similar to Example XI. S-car boxy-1,3 cyclopentadiene and an isomeric mixture of II are obtained in each case. octadienes are obtained as products. When sodium is replaced with other alkali metals or mixtures containing a major proportion of an alkali metal Table I Aryl compound: Aryl acid obtained such as lithium, potassium, cesium, rubidium, franciuni, Benzene ____________________ _. Benzoic acid. alloys of sodium and potassium or sodium and calcium, Mesitylene __________________ __ Trimesic acid. substantially identical results are obtained as in the ex Anisole____________________ __ Anisic acid. Indene _____________________ _- l-carboxy-indene. 10 amples given above. Equally good results are obtained when l-methylbuta diene, Z-methylbutadiene, 1,2-dimethylbutadiene, 1,3-di EXAMPLE VI Example I is repeated except that 2,3-dimethylbutadiene methylbutadiene, 1,4 - dimethylbutadiene, 1,1,4,4 - tetra methylbutadiene, 2,3-di-t-butylbutadiene, 1-phcnylbutadi— is employed in place of the butadiene and in the same 15 ene, 1,2-diphenylbutadiene, 1,3-diphenylbutadiene, 1,4~ molar proportions. A similar yield of the phenylacetic acid and the isomeric mixture of tetramethyloctadienes is also obtained. EXAMPLE VII Example II is repeated except that cumene is used in stead of toluene. In this example a total quantity of 325 parts of cumene are added to the reactor. More diphenylbutadiene, 1,3,5-hexatr'iene and 1,3,5-heptatriene are employed in the above reactions as the conjugated polyene reactant. Similarly, when o-xylene, m-xylene, 1,2,3~trimethyl benzene, 1,2,4-trimethylbenzene, a-methylnaphthalene, B methylnaphthalene, diphenylmethane, acenaphthene, phe nylacetylene, pyrrole, indole, quinoline, ?uorene, retene, propionitrile, acetylene and Z-methyl cyclopentadiene are over, following the removal of the active solvent, the re employed as the reactant to be transmetalated, the corre action mixture is heated for two hours at 140° C. instead of the 100° to 105° C. used in Example II. A satisfac 25 sponding metalated compound or its reaction product is tory yield of p-isopropylbenzoic acid and an isomeric mixture of octadienes are obtained. EXAMPLE VIII readily recovered in good yields. Similarly good results are obtained over a wide range of reaction temperatures. Reaction temperatures as low as —80° C. and as high as 40° C. give good yeilds of Example II is repeated except that after completing the aliphatic polyole?n hydrocarbons and transmetalated reaction the cooled reaction mixture is contacted with a stream of dry sulfur dioxide until the acid reaction to compounds when employing the low temperature process of this invention. In the preferred embodiment of the process of the invention, wherein the solvent is removed Congo paper disappears and the mass is further Worked up as described in Example II. a-Toluenesul?nic acid at a temperature below about 40° C. prior to complet and an isomeric mixture of octadienes are obtained in 35 ing the reaction at an elevated temperature, uniformly satisfactory yields. good results are obtained when subsequent reaction tem EXAMPLE IX Example II is repeated except that upon completing the reaction, the reaction mixture is treated with excess 40 benzonitrile. When the reaction is complete, the whole peratures as low as 50° C. and as high as 250° C. are employed to complete the reaction. EXAMPLE XIV mass is stirred for an hour at room temperature, then Example I was repeated except that sodium metal, poured into water and the organic phase is separated, boiled with dilute hydrochloric acid, cooled and extracted with ether. On distilling the ether extract, desoxybenzoin butadiene and sodium acetate were reacted in ethylene glycol dimethyl ether at 50° C. The sodium acetate was and an isomeric mixture of octadienes are obtained. metal. The OL-SOdlO sodium acetate Was produced in 92 percent conversion. Similar results are obtained with EXAMPLE X Example II is repeated except that upon completing employed in equal molar proportions with the sodium lithium and potassium metal and with the corresponding alkali metal salts of propionic, butyric and other acids the reaction, the reaction mixture is treated with an containing up to 20 carbon atoms. excess of formaldehyde. The mixture is cooled, hy drolyzed with dilute hydrochloric acid and the resulting mixture is extracted with ether. On distillation of the ethereal extract, phenethyl alcohol and an isomeric mix As is believed apparent from the above, the present invention provides a means of economically producing a wide variety of aliphatic polyole?n hydrocarbons and metalated compounds, many of which have heretofore ture of octadienes are obtained. been unavailable. More particularly, these aliphatic poly EXAMPLE XI Example I is repeated except that methylacetylene is metalated instead of toluene. In this example, 60 parts of isooctane are present in the reactor as the dispersion ole?n hydrocarbons and metalated compounds can be produced conjointly and over a relatively broad reaction temperature range. From the above, it is apparent that by varying the conjugated polyene or the compound to be transmetalated in the process, a wide spectrum of medium for the sodium and 22 parts of methylacetylene 60 aliphatic polyole?n hydrocarbons and metalated com are employed instead the 60 parts of toluene. An equally pounds can be produced as desired. The products can satisfactory yield of tetrolic acid is obtained as well as be used as important chemical intermediates in the manu a comparable yield of the isomeric mixture of octadienes. facture of valuable polymeric materials, plasticizers, syn thetic detergents, anti-foaming agents, solvents, adhesives, EXAMPLE XII 65 and many other valuable materials. Example X1 is repeated except that acetonitrile is This application is continuation-in-part of application metalated instead of methylacetylene. In this example, Serial No. 448,773 ?led August 9, 1954, now abandoned. 21 parts of acetonitrile are employed and the yield of I claim: products obtained are similar to those obtained in the 1. A transmetalation process for preparing aliphatic other examples. Cyanoacetic acid and an isomeric mix polyole?n hydrocarbons containing at least 8 carbon ture of octadienes are recovered as products. atoms and organo alkali metal compounds simultane ously, which comprises reacting (a) a dialkali metal poly EXAMPLE XIII ole?n compound containing at least 8 carbon atoms with Example XI is repeated except that cyclopentadiene is (b) an active hydrogen-containing organic reagent ca employed as the material to be metalated. In this ex pable of forming an alkali metal derivative thereof, 3,090,819 12 11s selected from the group consisting of (1) aryl hydrocar-p toward alkali metals, said dialkali metal polyole?n being bons, (2) acetylenic hydrocarbons, (3) cyclodienyl hy drocarbons, (4) aryl ethers, (5) aryl ?uorides, (6) an octa to dodeca polyene having an unsaturation ranging alkali metal salts of monocarboxylic acids containing between about 2 through 20 carbon atoms, and (7) sub from dienes to tetraenes, said reaction being initiatedat a temperature not greater than about 40° C. inva reaction _ medium comprising an ether selected from the groups ' consisting of aliphatic mono ethers having a methoxy group and an oxygen to carbon ratio of not less than 1:4, stituted hydrocarbons, wherein the sole substituent is a nitrilo group; which reagents are free from functional groups which are reactive toward alkali metals, said and polyethers derived from aliphatic polyhydric alcohols‘ having all of the hydroxyl atoms replaced by alkyl groups dialkali metal polyole?n hydrocarbon being an octa to dodeca polyene and having an unsaturation ranging from and mixtures thereof. ' ' 6. A transmetalation process for the simultaneous prep aration of an aliphatic polyole?n hydrocarbon containing dienes to tetraenes, said reaction being initiated at a temperature not greater than about 40° C. in a reaction at least 8 carbon atoms and an organo alkali metal com medium consisting essentially of a solvent selected from pound which comprises reacting (a) a dialkali metal poly the group consisting of ethers, acetals and tertiary amines; and recovering said polyole?n hydrocarbon and , ole?n with (b) an active hydrogen-containing reagent ca an alkali metal compound of said organic reagent as pable of forming an alkali metal derivative thereof, se lected from the group consisting of (1) aryl hydrocarbons, (2) acetylenic hydrocarbons, (3) cyclodienyl hydrocar 2. A transmetalation process for preparing aliphatic bons, (4) aryl ethers, (5) aryl ?uorides, (6) alkali metal polyole?n hydrocarbons containing at least 8 carbon atoms and organo alkali metal compounds simultaneously, which 20 salts of monocarboxylic acids, containing between about 2 through 20 carbon atoms, and (7) substituted hydrocar comprises reacting (a) a dialkali metal polyole?n com bons wherein the sole substituent is a nitrilo group, said pound with (b) an active hydrogen-containing organic reaction being initiated at a temperature not greater than reagent capable of forming an alkali metal derivative about 40° C. and in dimethyl ether. , thereof, selected from the group consisting of (1) aryl hy products of the reaction. . drocarbons, (2) acetylenic hydrocarbons, (3) cyclodienyl hydrocarbons, (4) aryl ethers, (5) aryl ?uorides, (6) al kali metal salts of monocarboxylic acids containing be tween about 2 through 20 carbon atoms, and (7) sub stituted hydrocarbons wherein the sole substituent is a 25 7. A transmetalation process for the simultaneous prep aration of an aliphatic polyole?n hydrocarbon containing at least 8 carbon atoms and an organo alkali metal com pound which comprises reacting (a) a dialkali metal poly-~ ole?n hydrocarbon compound with (b) an active hydro nitrilo group; which reagents are free from functional 30 gen-containing reagent capable of forming an alkali metal derivative thereof, selected from the group consisting of groups which are reactive toward alkali metals, said di (l) aryl hydrocarbons, (2) acetylenic hydrocarbons, (3) alkali metal polyole?n being an octa to dodeca polyene cyclodienyl hydrocarbons, (4) aryl ethers, (5) aryl ?uo and having an unsaturation ranging from dienes to tet rides, ( 6) alkali metal salts of monocarboxylic acids con-_ raenes, said reaction being initially carried out at a tem perature not greater than about 40° C. in a reaction 35 taining between about 2 through 20 carbon atoms, and ( 7) substituted hydrocarbons wherein the sole substituent medium consisting essentially of a solvent selected from is a nitrilo group, said reaction being initiated at a temper the group consisting of ethers, acetals and tertiary amines, ature not greater than about 0° C. and in a reaction me removing substantially all of said solvent at a temperature dium comprising an ether selected from the groups con below about 40° C. and thereafter increasing the reaction sisting of aliphatic mono ethers having a methoxy group temperature to between about 50° C. and 250° C. to com and an oxygen to carbon ratio of not less than 1:4 and plete the said transmetalation reaction. 3. A transmetalation process for preparing aliphatic polyole?n hydrocarbons containing at least 8 carbon atoms and organo alkali metal compounds simultaneously, which comprises reacting (a) a dialkali metal polyole?n com pound with (b) an active hydrogen-containing organic re agent capable of forming an alkali metal derivative there of, selected from the group consisting of (l) aryl hydro polyethers derived from aliphatic polyhydric alcohols hav aration of an aliphatic polyole?n hydrocarbon containing reacting in approximately equimolar proportions disodium at least 8 carbon atoms and an organo alkali metal com octadiene with sodium acetate in an ethylene glycol di ing all of the hydroxyl hydrogen atoms replaced by alkyl ' groups and mixtures thereof. 8. A process for the simultaneous preparation of octa-' diene and benzyl sodium which comprises reacting diso dium octadiene with toluene in a dimethyl ether reaction medium, said reaction being initiated at a temperature not greater than about 40° C. and thereafter recovering octa carbons, (2) acetylenic hydrocarbons, (3) cyclodienyl hy drocarbons, (4) aryl ethers, (5) aryl ?uorides, (6) alkali 50 diene and benzyl sodium as products of the reaction. 9. An improved process for the preparation of benzyl metal salts of monocarboxylic acids containing between sodium comprising reacting disodium octadiene with at about 2 through 20 carbon atoms, and (7) substituted least a stoichiometric quantity of toluene in a reaction me hydrocarbons wherein the sole substituent is a nitrilo dium consisting essentially of a solvent selected from the group, said reaction being initiated at a temperature not group consisting of ethers, acetals and tertiary amines, said greater than about 40° C. in a reaction medium consist— reaction being initiated at a temperature not greater than ing essentially of a solvent selected from the group con about 40° C., completing said reaction to form benzyl sisting of ethers, acetals and tertiary amines; and recover sodium. ing said polyole?n hydrocarbon and alkali-metal com 10. The process of claim 9 wherein the solvent is di pound of said organic reagent as products of the reaction. 4. The process of claim 3 further de?ned wherein the 60 methyl ether. 11. A process for the simultaneous preparation of octa dialkali metal polyole?n is disodiumoctadiene. diene and alpha-sodio-sodium acetate which comprises 5 . A transmetalation process for the simultaneous prep pound which comprises reacting (a) a dialkali metal poly 65 methyl ether reaction medium at a temperature of about 50° C., and thereafter recovering octadiene and alpha ole?n compound containing at least 8 carbon atoms with sodio-sodium acetate as products of the reaction. (b) an active hydrogen-containing organic reagent ca pable of forming an alkali metal derivative thereof, se lected from the group consisting of (1) aryl hydrocarbons, 12. A transmetalation process for simultaneously pre paring octadiene and an alpha-sodio-alkali metal salt of an (2) acetylenic hydrocarbons, (3) cyclodienyl hydrocar aliphatic monocarboxylic acid which comprises reacting bons, (4) aryl ethers, (5) aryl ?uorides, (6) alkali metal disodium octadiene with an alkali metal salt of an ali phatic monocarboxylic acid in an active solvent selected from the group consisting of ethers, acetals and tertiary amines, and thereupon recovering the octadiene and the bons wherein the sole substituent is a nitrilo group; which reagent is free from functional groups which are reactive 75 alpha-sodio~alkali metal salt of an aliphatic monocar salts of monocarboxylic acids containing between about 2 through 20 carbon atoms, and (7) substituted hydrocar "3,090,819 13 14 boxylic acid as products of the reaction; said reaction being initiated at a temperature not greater than about 2,171,867 2,171,871 2,773,092 2,816,917 2,881,209 40° C., said alkali metal salt of an aliphatic monocar boxylic acid containing from 2 to about 20 carbon atoms in the molecule and said disodiurn octadiene being formed by reacting butadiene with sodium in an active solvent as hereinabove de?ned. References Cited in the ?le of this patent UNITED STATES PATENTS 1,934,123 2,023,793 Hoffman et a1 __________ __ Dec. 7, 1933 Scott ________________ __ Dec. 10, 1935 ‘ _ _' Scott et a1 _____________ .__ Sept. 5, 1939 Walker _______________ __ Sept. 5, 1939 Carley et a1 ____________ __ Dec. 4, 1956 Hansley et a1. _., ____ __'___ Dec. 17‘, 1957 Nobis et a1. ___________ __ Apr. 7, 1959 OTHER REFERENCES Morton et al.: “Jour. Am. Chem. Soc.,” vol. 69, pp. 160 (1947). 10 Coates: “Quart. Reviews” (London), vol. 4, pp. 217 235 (1950), p. 220 only needed. Hansley: “Ind. & Eng. Chem,” vol. 43, No. 8, August 1951, pp. 1759 to 1766.