3,239,568 United States Patent Office Patented Mar. 8, 1966 2 the metal atom bonded to the oxygen atom of the alkoxide 3,239,568 molecule. MANUFACTURE OF ALKALMETAL (COAEPOUNDS Thus the alkali metallometallic alkoxides of this inven David O. De Pree and anaes D. Johnston, Baton Rotage, tion are bifunctional compounds-that is they contain two La., assignors to Ethyl Corporation, New York, N.Y., 5 reactive centers. One of the striking features of this in a corporation of Virginia vention is that in a reaction with a hydrocarbon halide or No Drawing. Filled Aug. 9, 1960, Ser. No. 48,356 hydrocarbon sulfate alkylating agent only the “metal 6 Claims. (C. 260-632) lo,' i.e.

This invention involves a process for the manufacture O of organic compounds, in particular, alkali metal alkox --M ides, which can easily be converted to the corresponding functional group reacts, and the "metallic,” i.e. alcohols. This invention is also concerned with bimetal lic organometallic compounds which are utilized in pre paring the alkali metal alkoxides of this invention. --OM Prior to this invention no satisfactory method was reactive center does not. known for increasing the molecular weight of metal alk Although the terms alkali metallometallic alkoxide and oxides using direct reactions of organic halides or organic metal alkoxide are employed throughout this specifica Sulfates. A process which employs hydrocarbon halides tion the process of this invention can be carried out using or hydrocarbon sulfates, and in particular, long chain hy 20 the corresponding alkenoxides and aryioxides, as these drocarbon halides, to produce alkali metal alkoxides of compounds are essentially equivalent to alkoxides for the increased chain length would be of particular value to purposes of this invention. the industry in providing a method for ultimately produc In carrying out the processes of this invention, it is ing the useful higher chain length alcohol itself. Such a preferred that the alkali metal alkoxide and alkali metal process has now been discovered. It is simple and eco 25 lometallic alkoxide contain sodium as the alkali metal nomical, and in its preferred form it utilizes readily constituent because of its ready availability, cheapness available, low cost hydrocarbon halide starting materials. and high reactivity. Furthermore, in order to produce Accordingly, it is an object of this invention to provide the most desirable alkali metal alkoxides from cheap raw a new and novel process for the direct preparation of materials having good reactivity it is preferred that the alkali metal alkoxides of increased molecular weight. 30 hydrocarbon portion of the alkylating agent contain from A particular object is to provide a process for the direct about 6 to about 20 carbon atoms and that the alkali preparation of alkali metal alkoxides of increased molec metallometallic alkoxide reactant contain from 1 to about ular weight from a reaction between an alkali metalio 4 carbon atoms. Thus the alkali metal alkoxides pro metallic alkoxide and a hydrocarbon halide. A still fur duced from these reactants by the process of this inven ther object is to porvide a process for the preparation of 35 tion contain about 7 through about 24 carbon atoms. A alcohols of increased molecular weight. Also an object more specific embodiment of this invention, and more of this invention, is to provide a process for the perpara fully demonstrative thereof, is the reaction of sodio-sodi tion of the alkali metaliometallic alkoxide utilized in the um methoxide with octyl bromide to produce sodium reaction with a hydrocarboa halide to prepare alkali metal nonoxide, which can be converted by hydrolysis to nonyl lic alkoxides of increased molecular weight. Other ob 40 alcohol. jects of this invention will be apparent from the follow In carrying out the reaction between an alkali metallo ing discussion. metailic alkoxide and said alkylating agents, the propor These and other objects of this invention are accom tions of the reactants employed, and the temperature of plished by providing a process for the preparation of the reaction are important and should preferably be main alkali metal alkoxides of increased molecular weight which tained within certain limits in order to achieve the de comprises reacting an alkali metallometallic alkoxide with sired alkali metal alkoixdes of increased molecular weight an alkylating agent, viz. hydrocarbon halide or a hydro in high yields and purity. In general between about 1. carbon Sulfate. and .5 equivalents of the alkoxide are employed per Also within the scope of this invention is a process for equivalent of hydrocarbon halide or hydrocarbon sulfate. the preparation of the above alkali metallometallic alk 50 The equivalent number of said halide is equal to the oxide which comprises reacting an alkali metal alkoxide number of carbon-halogen bonds contained therein; that Wtih a metalating agent at a temperature below the de of Said sulfate is equal to the number of carbon-sulfur composition temperature of the alkoxides formed and bonds contained therein, and said alkoxide has an equiv used as the reactant. In this embodiment alkali metals, alent number equal to the number of carbon-metal bonds alkali metal hydrides, or alkali metal amides are used as 55 therein. In order to avoid excessive by-product forma the metalating agent. tion and to achieve high yields, it is preferred to employ The term alkali metallometallic alkoxide, as used here essentially stoichiometric (i.e. equal equivalent) propor in, defines a bifunctional organometallic compound. One tions of the reactants based on one equivalent of hydro of the functional groups of this bifunctional compound is carbon halide or hydrocarbon sulfate for each equiavalent an alkali metal bonded directly to a carbon atom of the 60 of the alkali metallometallic alkoxide. The reaction tem alkoxide, i.e. perature employed is at least about -30° C. up to about the decomposition temperature of the reactants. How ever, it is generally preferred to employ a reaction tem --M perature of at least about 50° C. but below the decomposi and the other functional group is a metal bonded direct 65 tion temperature of the alkali metallometallic alkoxide in ly to the oxygen atom of said alkoxide, i.e. order to achieve a faster reaction rate and higher yields. Thus the process of this invention provides a direct route to alkali metal alkoxides of increased molecular weight --o-r from hydrocarbon halides. The product thereby pro In the term alkali metallometallic alkoxide the constituent 70 duced can be easily converted to the alcohol, or other designated as "metallo' is the alkali metal bonded direct valuable products. ly to a carbon atom and that designated as “metallic' is The alkali metallometallic alkoxides of this invention

3,239,568 3 4 are produced by a novel process which comprises reacting Example II an alkali metal alkoxide with a metalating agent selected from the group consisting of alkali metals, alkali metal To the reaction vessel described in Example I is added hydrides and alkali metal amides at a temperature below 1 mole of sodio-sodium methoxide as a 20 percent sus the decomposition temperature of said alkoxides. The 5 pension in n-octane. To this mixture is added slowly alkali metal alkoxide which is preferably employed in over a period of about 2 hours n-octylbromide, the tem this process is one which contains at least one hydrogen perature of the reaction mixture being maintained at atom on the alpha-carbon atom. Illustrative of such about 25° C. After the addition is completed the tem alkoxides are sodium methoxide, sodium ethoxide, Sodium perature of the reaction mixture is raised to about 100' butoxide and the like. Alkali metallometallic alkoxides C. and held there for about /2 hour to complete the re produced from such metal alkoxides have greater stability 10 action. The reaction mixture is cooled and the solids and thus give greater processing flexibility in the reaction (the sodium salt of n-nonyl alcohol and sodium bromide) with the hydrocarbon halide or hydrocarbon sulfate. are filtered off and hydrolyzed as in Example I. The The preferred metalating agents for use in preparing the water insoluble alcohol product (n-nonyl alcohol) is Sep alkali metallometallic alkoxides are sodium, sodium amide arated as a liquid. This material is then fractionated at and sodium hydride because of their cheapness, avail atmospheric pressure and a fraction boiling at about 230 ability or ease of preparation. Therefore, within the C. is collected and identified as n-nonyl alcohol, a water scope of this invention and a preferred embodiment insoluble, colorless liquid melting at -5° C. thereof is a process for the preparation of a-sodio-sodium Example III alkoxides which comprises reacting a sodium alkoxide, 20 containing at least one hydrogen atom on the C-carbon To a reaction vessel as described in Example I is added atom, with a metalating agent selected from the group 2 moles of o-sodio-sodium 2-butenoxide as a 20 percent consisting of sodium, sodium amide and sodium hydride suspension in mineral oil. The temperature of this mix- . at a temperature below the decomposition temperature of ture is raised to about 50° C. and thereafter the one mole Said alkoxides. of diethyl sulfate is added slowly over a period of about In general the reaction to produce alkali metallometal 1 hour after which addition the temperature of the re lic alkoxides is carried out in the absence of a Solvent, at action mixture is then raised to 150° C. for a period of a temperature ranging from about 50 to the decomposi about 72 hour in order to complete the reaction. Then tion temperature of the product produced and in the the reaction mixture is cooled, filtered under nitrogen and presence of good mixing or grinding, such as is obtained 30 the solids (the sodium salt of 4-hydroxy-2-hexene and in a balmill reactor. sodium sulfate) hydrolyzed. The product, 4-hydroxy-2- It is preferred to employ substantially stoichiometric hexene is thereby obtained. proportions of the reactants when carrying out the metala Example IV tion reaction. By stoichiometric proportions is meant To a reaction vessel, as described in Example I, is about 1 equivalent of the metalating agent per equivalent 3 5 added 1 mole of sodio-Sodium phenoxide as a 20 percent of metal alkoxide. It is also preferred that the reactants suspension in n-octane. The temperature of this mix be preponderantly anhydrous and, when a solid, prefer ture is raised to about 50° C. and thereafter one mole ably of a small particle size generally less than 100 mi of allyl chloride is added slowly over a period of about crons. Additionally the starting materials should be es 2 hours. Upon completion of the addition, the reaction sentially free of organometallic compounds or compounds 40 that would form organometallic compounds, other than mixture is heated to about 100° C. for about 45 min the product desired. In one embodiment the reactants utes and thereafter cooled to about 25° C. The reaction are mixed and ground in a balmill reactor under an mixture containing the sodium salt of p-allyl phenol is inert atmosphere and volatile by-products are contin then hydrolyzed and the organic layer separated. The uously removed. The desired alkali metallometallic alk Solvent is then distilled off from the organic layer to oxide is thereafter recovered from the ball mill reactor. leave a crystalline residue. This residue is then re A particular advantage of this novel process for pre crystallized from ethanol and the product p-allyl phenol paring alkali metallometallic alkoxides is that the de is obtained. sired product is obtained substantially in its pure form Example V and in high yield. Another advantage of this process is 50 To a reaction vessel provided with means for heating, that it employs only one equivalent of metal of such cooling, stirring, refluxing, continuous addition of re cheap metalating agents as, for example, Sodium. actants and introduction of inert atmosphere is added 2 The novel reaction of an alkali metallometallic alkoxide moles of o-sodio-sodium ethoxide as a 20 percent sus with a hydrocarbon halide or sulfate is more fully demon pension in mineral oil. The reaction mixture is cooled strated by the following examples. In these examples all to -30 C. and one mole of dimethyl sulfate added parts and percentages are by weight unless otherwise thereto. This temperature is maintained for a period of specified. 2 hours to complete the reaction. The reaction mixture Example I containing the sodium salt of isopropyl alcohol is hy drolyzed with 2 moles of water, followed by fractiona To a reaction vessel provided with means for heating, 60 tion of the alcohol product from the mineral oil diluent. cooling, refluxing, stirring, addition of reactants and for In this manner is produced isopropyl alcohol, a color introduction of an inert atmosphere is added 1 mole of less liquid having a melting point of -88 C. and a sodio-sodium methoxide as a 20 percent suspension in boiling point of 82.3 C. mineral oil. This mixture is heated to about 50 C. and In addition to the hydrocarbon halides and hydrocar thereafter 0.5 mole of 1,4-dichlorobutane is added over 65 bon Sulfates employed in the above examples other hydro a period of 2 hours. Upon completion of the addition, carbon halides and hydrocarbon sulfates can be employed the temperature is raised to 100° C. for /2 hour to com in this invention. In general halogen, or sulfate, con plete the reaction. The reaction mixture is then cooled taining aliphatic, cycloaliphatic and aromatic hydrocar and the solids (the sodium salt of 1,6-hexane diol and bons, usually containing up to about 20 carbon atoms, sodium chloride) are filtered under nitrogen atmosphere can be employed. Therefore the aliphatic halides and and, while maintaining the inert atmosphere, are hydro aliphatic sulfates can contain 1-20 carbons; the cyclo lyzed with water. The water solution is fractionated by aliphatic halides and cycloaliphatic sulfates, 3-20 car first removing the water and then distilling the product bons; and the aryl halides and aryl sulfates, 6-20 carbon produced (1,6-hexane diol) over at about 250° C. The atoms. The halogens contained in the hydrocarbon hal. product is a solid at 25 C. and melts at 42 C. 75 ide can be fluorine, chlorine, bromine, iodine and asitine 3,239,568 5 6 although the last is rarely employed for economic reasons. metallated product produced, nevertheless, only employs In most cases the halides of this invention contain 1-2 one equivalent of metal in the metalation of a carbon halogens which preferably are chlorine or bromine or atom. Thus this embodiment is consistent with the stoi both because of their reactivity and low cost. chiometry described hereinbefore. To more fully demonstrate the process for preparing The hydrocarbon halides and hydrocarbon sulfates em alkali metallometallic alkoxides the following examples ployed pursuant to this invention include alkyl halides, in which all parts and percentages are by weight are aralkyl halides, alkenyl halides, aralkenyl halides, cyclo presented. alkyl halides, cycloalkenyl halides, aryl halides, akaryl Example VI halides and the like hydrocarbon halides as well as the O corresponding hydrocarbon sulfates. In the preferred Into a ball mill, provided with means for heating and cases the hydrocarbon halide is one which has at least having about a 30 percent ball charge (total apparent one hydrogen atom on the halogen substituted carbon volume of mill occupied by the balls) and, furthermore, atom since these halides exhibit good stability and re having means for removal of off gas, are added 200 activity. The hydrocarbon halides and hydrocarbon sul parts of anhydrous sodium chloride and 46 parts of so fates of this invention can be methyl chloride, dimethyl dium metal. This mixture is heated and ground to about sulfate, ethyl bromide, diethyl sulfate, 1-propyl fluoride, 150° C. for 4 hour and thereafter cooled to 25 C. di-1-propyl sulfate, 2-butyl iodide, di-2-butyl sulfate, Thereafter, 32 parts of methanol is added under nitrogen 2-penty astatide, di-2-phenyl sulfate, 1-eicosyl chloride, atmosphere, while grinding is effected over a period of and di-1-eicosyl sulfate; and the branched chain deriva 1 hour. After this time hydrogen evolution ceases and 20 tives thereof; dichloromethane, dibromoethane, diethyl the mill is then heated with grinding to 170° C. with sulfate, 1,3-diiodobutane, di-butyl sulfate, 1,5-difluoro evolution of additional hydrogen. The mill is then eicosane, trichloromethane; 1,4,10-triiodoeicosane; also cooled and the product sodio-sodium methoxide is re mixed alkyl halides such as the chlorobromoethanes and moved from the ball mill in good yield and purity. the like; mixed hydrocarbon sulfates like methylethylsul Example VII 25 fate, n-propyl-n-butyl sulfate and the like; alkenyl halides A ball mill equipped with means for heating, removal and alkenyl sulfates such as 3-chloro-1-propene, di-1- of off gas and having approximately a 30 percent ball propeny sulfate, 4-bromo-1-decaptene, di-1-decapentenyl charge is charged with about 1.4 moles of sodium amide sulfate; 4,6-dichloro-1-hexane, di-1-hexenyl sulfate; 3,3,4- and 1 mole of sodium 2-butenoxide. Heating and grind trichloro-1-butene, di-1-butenyl sulfate, 20-chloro-1-eico ing is commenced and the temperature is maintained at 30 sene, di-1-eicosenyl sulfate, and the like. about 120° C. to about 180 C. for a period of 2 hours. Illustrative of the cyclic halides and cyclic sulfates used The ball mill is then shut down and cooled and the in this invention are 1-chlorocyclopentane, dicyclopenty product o-sodio-sodium 2-butenoxide is obtained in good sulfate; 1,4-dichlorocyclohexane, dicyclohexyl sulfate; yield. 1,3,7-tribromocyclooctane, dicyclooctyl sulfate, 1-iodo 35 cyclobutane, dicyclobutyl Sulfate, 1-fluorocyclopentane, 4 Example VIII (2-chlorododecyl) octyl chloride, cyclopentadienyl chlo To a ball mill, as described in Example VI, is added ride, dicyclopentadienyl sulfate, cyclohexadienyl iodide, 200 parts of sodium chloride, 46 parts of sodium. The cyclohexadienyl sulfate, cyclooctadienyl dichloride, di materials are mixed and ground while introducing hy cyclooctadienyl sulfate, 3-chloro-1-cyclohexyne, dicyclo drogen at a temperature of about 200 C. to 300° C. 40 hexynyl sulfate, 2-phenyl-1-chloroethane, di-2-phenyl When hydrogen uptake ceases the mill is cooled and ethyl sulfate, chlorobenzene, diphenyl sulfate, iodoben 74 parts butanol are added under grinding at about 25 zene, bromonaphthalenes, naphthyl sulfates, chlororan C., this temperature being maintained until hydrogen thracenes, anthracyl sulfates, benzyl chloride, dibenzyl evolution ceases. The reaction mixture is then heated sulfate p-methyl chlorobenzene, 2-(2-chloroethyl)-8-octa under grinding to about 180 C. until the newly com naphthalene, 1-chloro-2-butenyl benzene, and the like. menced hydrogen evolution ceases. The mill is then The hydrocarbon halides and hydrocarbon sulfates for shut down and cooled and the product o-Sodio-Sodium use in practicing this invention can be substituted as well butoxide is removed. as unsubstituted. When substituted, the substituents are Example IX groups which activate the hydrocarbon halide or hydro carbon sulfate. Such activating groups are ether, sulfate, To a reaction vessel provided with means for heating, tert-amino, tert-phosphino, tert-arsino, thio ethers, silyl, stirring, cooling, refluxing, addition of reactants and vent stannyl, plumbyl, nitrosyl, and the like. ing of off gases, is added 2 moles of Sodium amide as A preferred class of hydrocarbon halides for use in this a 20 percent suspension in a mineral oil solvent. This invention are those which are resistant to dehydrohalo mixture is heated to about 30° C. and one mole of decanol 55 genation, such as hydrocarbon halides having at least is added under high speed stirring over a period of about one hydrogen on the halogen substituted carbon atom. a hour. The reaction temperature is then raised to about This class of dehydrohalogenation resistant hydrocarbon 100° C. and maintained at this temperature for a period halides finds particular applicability in the instant process of 2 hours. Thereafter the reaction mixture is cooled, when higher temperatures are employed, viz. temperatures filtered to obtain the desired product C-Sodio-Sodium 60 substantially above 140 C. Typical, but non-limiting decoxide. examples of these preferred hydrocarbon halides include Example X benzyl chloride, n-butyl bromide, allyl chloride, octyl A balmill provided with means for heating and re bromide, hexenyl chloride, beta-cyclohexylethyl bromide, moval of off gases is charged with one mole of Sodium octenyl chloride and the like hydrocarbon halides having phenoxide and one mole of sodium. Heating and grind 65 up to about 18 carbon atoms, and similar compounds in ing is commenced and the temperature raised and main which the halide is chlorine, bromine, iodine or fluorine. tained at approximately 200° C. for a period of 2 hours. In this class of organic halides, the iodides and bromides Thereafter the balmill is shut down, the product cooled are especially preferred since they are more resistant to and the desired product, sodio-sodium phenoxide, is ob dehydrohalogenation. Many other examples will be evi tained in good yields. 70 dent to those skilled in the art. Thus, in any of the Although it is generally preferred to employ the metal examples presented above, hexenyl chloride, n-butyl bro alkoxide as described hereinabove it is now obvious that mide, allyl chloride and the like can be substituted for the free alcohol can also be employed to produce the the hydrocarbon halide employed in the reaction with metal alkoxide in situ. Such an embodiment, although the attainment of similar results. utilizing 2 equivalents of metal per each equivalent of 75 In addition to the hydrocarbon halides and hydrocarbon 3,239,568 7 s sulfates discussed above, the process of this invention alkyl radicals which form an amine derivative in the re employs novel alkali metailometallic alkoxides. These action which boils at about 100° C. or less and is rela alkali metallometallic alkoxides are more fully demon tively stable under reaction conditions. Thus, for ex strated by the following illustrative formula: ample, A and B can be the radicals methyl, ethyl, iso 5 propyl, and the like. The use of the metal amides, or the substituted metal amides, which will result in a de wherein M and M' are alkali metals and furthermore M rivative having a boiling point below about 100° C. and can in addition be a polyvalent metal Such as the alkaline is comparatively stable under reaction conditions is pre earth metals, the III-A metals (Periodic Chart of the ferred since the derivative can be readily and rapidly re Elements, Fischer Scientific Company, 1955)--in short O moved from the reaction mixture. Rapid removal of M' can be any alkali or polyvalent metal which will form the derivative maintains the course of the reaction toward a metal alkoxide. R is a hydrocarbon group, in most the formation of the metailometallic alkoxide. cases being an alkyl, aryl or alicyclic radical, containing Illustrative of these metal amides are lithium amide, from about 1 through about 20 carbon atoms; and x is Sodium amide, potassium amide, rubidium amide, cesium an integer equal to the valence of the metal M'. It amide and francium amide; lower alkyl amides such as should be noted that although M' can be a polyvalent N-Sodium propyl amide, N-sodium dimethylamide, N metal, as defined above, it is especially preferred that lithium butyl amide, N-potassium diethylamide and the M' be an alkali metal which can be the same or different like. from the alkali metal M. (By metal is meant all the Alkyl metal hydrides utilized in the metallation process metals of Group I-A of the Periodic Chart of the Ele 20 of this invention are metal hydrides such as sodium ments.) The reason for this preference is due to the hydride, potassium hydride, rubidium hydride, cesium comparative ease with which the alkali metal alkoxides hydride, lithium hydride and francium hydride. can be formed and, furthermore, due to the generally In addition to alkali metal amides and alkali metal hy wide availability and low cost of such alkali metals as cirides, the alkali metals form a third class of metalating Sodium which is herein especially preferred. It is pre 25 agents utilized in the process of this invention. These ferred that the hydrocarbon group, R, contain through alkali metal metalating agents are the metals of Group 4 carbon atoms because of the cheapness and ready avail I-A of the Periodic Chart of the Elements (Fischer ability of the alcoholate starting materials used in prepa Scientific Company, 1955) and include lithium, sodium, ration of metallometallic alkoxides of such carbon con potassium, rubidium, cesium and francium, with sodium tent. being the most highly preferred. A preferred embodiment of this invention is the em In preparing alkali metallometallic alkoxides, the ployment of an alkali metallometallic alkoxide reactant metalation is conducted at a temperature sufficient to in a reaction with an alkylating agent of this invention initiate the reaction, generally about 50° C. up to the wherein said reactant has the metal, M, substi decomposition temperature of the metal alkoxide utilized tuted on the terminal carbon atom. Such alkali metal 3 5 in the reaction (generally temperatures no higher than lometallic alkoxides, when reacted with the hydrocarbon 300° C. are utilized). It is preferred to conduct the re halide or hydrocarbon sulfate alkylating agents produce action at a temperature ranging from about 70° C. to highly desirable primary metal alkoxides. When the about 200° C. In some cases it is desirable to employ metal M is substituted on the carbon atom other than a temperatures approaching the decomposition temperature terminal carbon atom, Secondary and tertiary metal 40 of the product produced, i.e. within about 30 degrees of alkoxides are produced. Said decomposition temperature. This is especially true A special class of alkali metallometallic alkoxides is in the case where a metal hydride is employed as the re demonstrated by the following general formula: actant. Furthermore, an excess of either reactant (i.e. metalating agent or metal alkoxide) can be employed, However, if an excess of one of the reactants is employed it is preferable that the metal alkoxide be in excess so that the metalating agent will be essentially quantitatively wherein M and M' are alkali metals and can be the same consumed. However, generally it is preferred to employ or different, and R is a hydrogen or a hydrocarbon group, a stoichiometric proportion of the reactants up to a small as defined hereinabove. These alkali metallometallic 50 eXcess (e.g. up to about 1.4 to 1 equivalents of alkoxide alkoxides are preferred because of their stability and high to metalating agent) for economic reasons. By stoichio reactivity in a reaction with a hydrocarbon halide or a metric quantities is means one equivalent of substitutable hydrocarbon sulfate. More fully illustrative of this latter hydrogen in the metal alkoxide reactant per equivalent class of alkali metallometallic alkoxides are sodio-sodium of metal in the metalating agent. methoxide, c-Sodio-sodium ethoxide, c-sodio-sodium In preparing alkalimetallometallic alkoxides, the propoxide, ox-Sodio-Sodium butoxide, ox-Sodio-sodium de particle sizes of the reactants is very important. In gen coxide, ox-sodio-sodium-eicosoxide, oz-Sodio-potassium eral, it is preferred to employ particle sizes below about methoxide, ox-potassio-lithium propoxide, oz-Sodio-rubidium 100 microns and usually below about 50 microns. The ethoxide, c-sodio-cesium ethoxide, a-rubidio-Sodium hex Smaller the particle size, the shorter the reaction period. oxide and the like. 60 Thus, best results are obtained when the particle size of The metal amides used in this invention to form the the reactants is less than 10 microns. In conducting the above described metallometallic alkoxides can be repre process, the reactants can be preground and premixed sented by the following general formula: and fed continuously to a heated surface. However, it A. is preferred to conduct the reaction while grinding and M mixing the reactants and applying heat. Thus, it should N be understood that the reactants need not be preground BM w. or premixed, but can be fed to the reactor Separately in wherein M is an alkali metal, A and B can be the same larger particle sizes and mixed and ground in situ. This or different and are hydrogen or lower alkyl radicals, and is particularly described when the agitation provided w is a small whole number. These metal amide deriva 70 in the reactor is of the type to provide grinding of the re tives are readily prepared by reacting an amine with the action mixture during the course of the reaction. Em metal in the presence of a conjugated polyene. For ex ploying the technique of the grinding along with the agi ample, N-sodium propyl amide is prepared by reacting tation provides more complete reaction. One highly pre n-propyl amine with finely divided sodium in the presence ferred method of doing this is to employ a ball mill as a of butadiene. In general, it is preferred to employ lower reactor, although any tumbling mill can be employed 3,239,568 O such as a pebble mill, rod mill, tube mill or compartment chain alcoholate functional groups as side chains on the mill. Other milling apparatus which will now be evident polymer. The metal alkoxides can also be reacted to to those skilled in the art can be also employed. form high molecular weight esters employing conven Preparation of alkali metallometallic alkoxides should tional esterification techniques. be conducted in an inert atmosphere such as argon, Having described the process of the present invention Initrogen, krypton, and the like. It is preferable that the it is not intended that it be limited except as set forth inert atmosphere be pre-purified so as to be substantially in the following claims. free of impurities such as oxygen and moisture, since We claim: these impurities may be taken up in the product. For 1. A process for the preparation of an alkali metal alk some purposes it is desirable to conduct the reaction 10 oxide which comprises contacting under inert, substan under an inert liquid blanket. One of the purposes of tanially anhydrous and oxygen-free conditions an alkali Such an embodiment is to avoid oxygen contamination metallometallic alkoxide with an alkylating agent; at a by impurities in the flushing gas. This inert liquid temperature ranging from about -30° C. up to the de blanket is generally a high boiling paraffinic hydrocarbon composition temperature of the alkali metallometallic such as mineral oil. The reaction is also conducted at 5 alkoxide; said alkali metal alkoxide so produced having atmospheric or sub-atmospheric pressures. Sub-atmos the formula pheric pressures have the advantage of enhancing re moval of any volatile by-products thus obtaining more rapid reaction and more complete shifting of the equi f librium. 20 R--OM The process for preparing alkali metallometallic alk R oxides is admirably suited to continuous methods. For example, the reactants separately or together in the said alkali metallometallic alkoxide having the formula proper proportions are continuously ground to desired particle size, transmitted to a heated movable reactor 25 R surface, the volatile by-product is removed and recovered M--OM for recycling to the preparation of the metal amide or R derivative thereof, and the product is continuously dis charged from the reactor. This and other modifications and said alkylating agent having the formula will now be evident to those skilled in the art. 30 In reacting the above described alkali metallometallic RX alkoxides with a hydrocarbon halide or hydrocarbon sul wherein R is selected from the group consisting of hydro fate to produce metal alkoxides of increased molecular gen and alkyl radicals containing from 1 to about 20 car weight, temperatures ranging from about -30° C. up to bon atoms, R’ is a hydrocarbon radical containing from the decomposition temperature of the alkoxides are em 35 1 to about 20 carbon atoms, M is an alkali metal and X ployed. (Generally, temperatures no higher than 200° C. is selected from the group consisting of halide radicals however are employed.) Furthermore, the pressure of and the sulfate radical. the reaction is not critical except in that pressure pro 2. A process for the preparation of an oc-alkylated vides a convenient means for obtaining in certain in alkali metal alkoxide which comprises contacting under stances desired temperature conditions. Thus atmos 40 inert, substantially anhydrous and oxygen-free conditions pheric pressure can be utilized and other pressures have an alkali metal alkoxide having a hydrogen atom on the no particular effect upon the reaction. Sub-atmospheric ox-carbon atom with a metalating agent selected from and Super-atmospheric pressures can however be em the group consisting of (1) alkali metals, (2) alkali ployed. metal halides, and (3) alkali metal amides at a tempera As indicated in the examples, diluents are generally ture of from about 50 C. up to the decomposition tem employed in carrying out this embodiment of the inven 45 perature of said alkoxide, said metalating agent and said tion. Such diluents ordinarily are not required when the alkoxide having a particle size below about 100 microns, hydrocarbon halide or hydrocarbon sulfate is a liquid. and thereafter contacting the alkali a-metallometallic However, for more efficient agitation and contact of the alkoxide thereby produced with an alkylating agent se reactants, diluents are generally employed. The criteria lected from the group consisting of hydrocarbon halides for choice of diluents are that they be liquid under the and hydrocarbon Sulfates at a temperature ranging from reaction conditions and substantially inert to the re about -30° C. up to the decomposition temperature of actants. Such diluents are parafiinic hydrocarbons such the alkali a-metallo-metallic alkoxide. as mineral oil petroleum ether, etc. Other typical ex 3. A process for the preparation of an alkali co-metallo amples are pentanes, octanes and the like containing up metallic alkoxide which comprises contacting an alkali to about 18 carbon atoms. metal alkoxide having a hydrogen atom on the g-carbon The proportions of alkylating agent and alkalimetallo atom with a metalating agent selected from the group metallic alkoxide employed generally range from stoichi consisting of (1) alkali metals, (2) alkali metal hydrides, ometric up to a small excess of the alkali metallometallic and (3) alkali metal amides at a temperature of from alkoxide. By stoichiometric proportions is meant approxi 60 about 50° C. up to the decomposition temperature of mately one equivalent of metal as the metallo substituent said alkoxide and under inert, substantially anhydrous and of the metallometallic alkoxide to one equivalent of the oxygen-free conditions said metalating agent and said hydrocarbon halide or hydrocarbon sulfate. When an alkali metal alkoxide having a particle size below about excess of the alkoxide is employed generally no greater 100 microns. excess than about 1.5:1 equivalents of alkoxide to hydro 65 4. A process for the preparation of sodium alkoxides carbon halide or hydrocarbon sulfate are utilized. which comprises contacting under inert, substantially an The metal alkoxides of increased molecular weight hydrous and oxygen-free conditions a sodio-sodium-alk prepared by the process of this invention are of consider oxide with an alkylating agent at a temperature ranging able and wide-spread utility. As discussed above these from about -30° C. up to the decomposition tempera metal alkoxides can be hydrolyzed to produce alcohols of 70 ture of said sodio-sodium-alkoxide; said sodium alkoxide increased molecular weight. They can also be utilized in So produced having the formula the preparation of detergents or as monomers in the R preparation of high molecular weight polymeric struc tures. The unsaturated metal alkenoxides can be po R--o Na lymerized to form polyethylenic type polymers with long 75 R

3,289,568 2 said Sodio-Sodium-alkoxide having the formula stantially anhydrous and oxygen-free conditions a sodium R alkoxide containing a hydrogen atom on the c-carbon atom with sodium at a temperature of from about 50 C. Ni--ON up to below the decomposition temperature of said alk R 5 Oxide, said sodium and said sodium alkoxide having a said alkylating agent having the formula particle size below about 100 microns. RX References Cited by the Examiner wherein R is selected from the group consisting of hydro UNITED STATES PATENTS gen and alkyl radicals containing from 1 to about 40 O carbon atoms, R is a hydrocarbon radical containing 2,069,403 2/1937 Cunningham. from about 6 to about 20 carbon atoms and X is a halide 2,715,057 8/1955 Pryde. radical. 2,873,290 2/1959 Esmay et al. 5. A process for the preparation of nonyl alcohol OTHER REFERENCES which comprises contacting sodio-Sodium methoxide with 5 Bruhl et al.: "Ber. Deut. Chem.” vol. 24, pp. 649-650 octyl bromide under inert, substantially anhydrous and (1891). oxygen-free conditions at a temperature ranging from Finar: "Organic Chemistry, vol. 1, 3rd ed. (1959), about -30° C. up to the decomposition temperature of page 218 (one page), Longmans, Green and Co. (Lon said sodio-Sodium-methoxide to form sodium nonoxide don). and thereafter contacting said nonoxide with water, said 20 Wagner et al.: "Syn. Org. Chem." N.Y., J. Wiley & process being conducted at a temperature of up to about Sons, Inc., 1953, pp. 10, 226. 100° C. 6. A process for the preparation of an a-sodio-sodium LEON ZITVER, Primary Examiner. alkoxide which comprises contacting under inert, Sub CHARLES B. PARKER, Examiner.