United States Patent Office Patented Mar

2,826,598 United States Patent Office Patented Mar. 11, 1958 2 whelming majority of cases have the empirical formula 2,826,598 me.olefin.R (wherein R has the above-indicated mean PRODUCTION OF ORGANIC COMPOUNDS OF ing); and in the case of diolefins have the empirical ALUMNUMAND BERYLLUM formula mediolefin.R or me-diolefin.R. (correspondingly in the case of poly-olefins). everal olefin molecules can, Karl Ziegler and Hans-Georg Gellert, Mulheim (Ruhr), however, be added to one me.R, thus giving products of Germany the empirical formula me(olefin).R, wherein m repre No Drawing. Application June 17, 1952 sents a small whole number from 1 to about 6. Serial No. 294,065 The process will first be illustrated by a simple ex 0. ample: A solution of aluminum hydride in ether (prefer Claims priority, application Germany June 21, 1951 ably 0.6 molar) is introduced into an autoclave and dry, air-free ethylene is forced in, preferably in a multiple 31 Claims. (C. 260-448) of the equivalent quantity of 3 mols. The mixture is This invention relates to improvements in the produc then heated cautiously to approximately 70-80 C.; at tion of organic compounds of aluminum and beryllium. a higher temperature there would be the danger of the It is based on the discovery that compounds of the general aluminum hydride decomposing. A fall in pressure is formula Me(R), wherein Me represents one of the two very soon observed, and the pressure again becomes above metals, and R represents a hydrogen atom or a approximately-constant when 3 mols of ethylene have monovalent saturated aliphatic radical or aromatic radi 20 been taken up per mol of aluminum hydride. When cal in any desired combination, and n represents the the excess of ethylene is blown off, the autoclave is valency of the metal, can form addition products with emptied in an atmosphere of nitrogen and the reaction olefins. The compounds of the type Me(R) can also be product is worked up, the known compound aluminum employed for this in the form of their molecular com triethyl etherate Al(CH5)3%O(C2H5)2 can very readily pounds with ethers, thioethers or tertiary amines, and be isolated in almost quantitative yield. also in the form of their complex compounds with alkali Thus the following reaction has taken place: hydrides, alkali alkyls and alkali aryls. The starting materials for the process of the invention, therefore, H CH-CH, include the following: Ali --3CH=CH=All-CH-CH 30. YH. CH-CB AlH, aluminum hydride The reaction takes an entirely similar course when a LiAlH4 lithium aluminum hydride start is made from an ethereal solution of aluminum AHR, aluminum alkyl dihydrides lithium hydride. The known lithium aluminum tetra AlHR2, aluminum dialkyl hydrides ethyl crystallizes from the reaction mixture directly, or AlR3, aluminum trialkyls (-aryls) on concentration in an atmosphere of nitrogen. It proves LiAlra, lithium aluminum tetraalkyls to be completely identical with a product produced from NaAlHR3, sodium aluminum trialkyl hydrides, and simi lithium ethyl and aluminum tri-ethyl. lar compounds, also aluminum trialkyl etherates BeH, beryllium hydride All the olefins of the type R-CH=CH, and BehR, beryllium alkyl hydrides R BeR, beryllium dialkyls 40 Yo-OH, Beryllium dialkyl etherates p? and similar molecular compounds of tertiary amines and (R' and R'=alkyl, alkenyl, aralkyl or cyclo-alkyl, R' thioethers. and R' being the same or different) can be converted The chemical compounds formed in accordance with 45 with aluminum hydride in a wholly analogous manner the invention are organic compounds of aluminum and into the corresponding aluminum compounds. beryllium, including molecular compounds thereof with The following table sets out aluminum compounds ethers, thioethers, tertiary amines and including complex produced in this way, almost all of which are new: compounds thereof with alkali hydrides, alkali alkyls and alkali aryls. In these compounds at least one valence bond 50 of the metal aluminum or beryllium is bound to a group Starting material Product (as the etherate) having the general formula (R),R, in which R is a bi valent hydrocarbon radical such as an alkylene, alkenyl CH, CH=CH, (CH, CH, CH)3Al ene, aralkenylene, or cyclo alkylene radical, and R may CH, CH, CH, CH=CH, (CHs. CH2. CH. CH, CH2)Al be hydrogen, monovalent saturated aliphatic radicals, or 55 CE aromatic radicals. The other valences of the aluminum Yo-CH, ((CH3). CH.CHls Al of beryllium metal may be bound with the same or differ ent groups having the same general formula (R).R, ch? or may be bound by R or R' in any combination. In CE Co the formula, m is a number from 1 to 6. 60 Unsaturated hydrocarbons can be added in simple Yo-CE, on-on whole-number proportions to all these compounds. C cit? 3 f CH;(CH.). CH=CH, ICH.(H)10. CHs Al Me 2. 65 { X-CH=CH, KD-CE.Chal is one equivalent of the metal Me of the valency in and CH.(CH) CE (CH), is designated by "ne' 2C-CE, CH-OH, Al (M=m) 70 CH. (CH) CH.(CH2) 3 the products of the process of the invention in the over These compounds are obtained in the first place in the 2,826,598 3 4. form of their very stable etherates. If it is desired to this possibility of converting the very readily accessible obtain the ether-free products, which differ from the and very stable aluminum trialkyl etherates into ether etherates in many respects, for example in their catalytic free compounds represents an important application of effectiveness, then one of the following processes must be the process of the invention. adopted: (3) According to another modification of the process, (1) The aluminum hydride is freed as far as possible the reaction between the olefin and aluminum hydride is from ether before reaction with the ethylene. For this interrupted before 3 molecules of the olefin have been purpose the ethereal solution of aluminum hydride is taken up. For example, when ethylene is used, if the evaporated until the hydride remains as a solid residue reaction vessel is cooled at the instant at which the fall and this residue is freed from ether as far as possible by li) in pressure indicates that 1 to 1.5 mols of ethylene have careful heating in vacuo. As described by Finholt, Bond been used up, then the reaction product consists mainly and Schlesinger (Journ. Am. Chem. Soc., vol. 69, 1202 of mixtures of HaAl(CH5) and HAl(CH5)2, from (1947)) it is possible to proceed in this way to a molecular which the compound HAl(CH5)2 first passes over on ratio of hydride to ether of approximately 5:1. Under careful distillation in as high a vacuum as possible (color the above-described conditions, this solid aluminum less liquid of density d420=0.808 and refractive index hydride also adds on olefins to form aluminum trialkyls, n20= 1.47396, which ignites spontaneously in the air). which are then largely free from ether. In this case the These alkyl aluminum hydrogen compounds do not form solid hydride can be reacted directly with the olefins at stable etherates. They are also much more stable to temperatures of about 70 to 90° C. In many cases, for heat than is aluminum hydride. It is, therefore, pos example in the case of propylene, this is not advisable, 20 sible to obtain these products completely free from however, since the addition of aluminum hydride to olefins ether by suitable heating in high vacuo or , also by takes place with spontaneous evolution of heat, so that distillation in high vacuo. and then to convert them with unless one works very carefully, a lively spontaneous freshly added olefins into ether-free aluminum trialkyls. reaction can set in with increase of temperature to more It is obvious that mixed aluminum trialkyls can also be than 100. C., which then destroys a part of the aluminum 25 produced via these compounds, by choosing for employ hydride by decomposition into hydrogen and aluminum ment in the second stage. a different olefin from that em and it is, therefore, advantageous to suspend the alumi ployed in the first stage. num hydride in pentane or another indifferent solvent. In this case it is not necessary, however, to produce It has also proved advantageous to convert the solid the alkyl aluminum hydrogen compounds in the above aluminum hydride prior to the reaction into a very fine 30 described way from olefins and aluminum hydride. These suspension in one of these indifferent solvents, for ex products can also be obtained in other ways. Since these ample, by grinding in a ball mill. From this suspension, compounds, as already mentioned, are considerably more even the last traces of ether can be removed, if desired, stable to heat than is aluminum hydride itself, by means by distilling off the suspension medium, while continually of them it is also possible to link secondary residues by making up the evaporated liquid, so as to obtain prac means of 1.2-disubstituted ethylenes with aluminum in tically ether-free aluminum trialkyls after the reaction good yields to form mixed aluminum trialkyls. Thus, with the olefin. This distillation operation can also be there are no special difficulties in producing aluminum carried out under reduced pressure, especially when a diethyl-secondary-butyl from (C2H5)2AIH and solvent is employed, having a boiling point higher than 80 C., for example, toluene, xylene, decahydro 40 CH3CH=CHCH naphthalene, or the like. (2) Instead of working in ethereal solution, it is pos in an autoclave (72 hours, 70° C. in the absence of sible to obtain aluminum alkyls free from ether by solvents). proceeding as follows: An ethereal solution of a complex In all the above-considered reactions the residue al-H aluminum alkali tetra-alkyl is first produced either by 45 is added on to olefins, the symbol "al' representing one starting from an ethereal solution of lithium aluminum third of a molecule of aluminum. The al-C group, how hydride, and not from an ethereal solution of aluminum ever, which is characteristic of aluminum trialkyls and hydride, for the addition of the olefin, or by first adding aluminum triaryls, has the same power of forming addi the olefin to ethereal aluminum hydride and then con tion compounds with olefins. Thus, the higher aluminum verting the aluminum trialkyl in the solution to aluminum 50 compounds trialkyl etherate. Thereafter, this etherate is converted into the complex alkali trialkyl aluminum hydride by the CHCHCH, CH, CHCH. CII2. CH3 addition of a calculated quantity of a suspension of All-CH2CH2. CH2CH3 lithium hydride or sodium hydride. On subsequent Alcil,CHs C2Es treatment with the olefin, the complex alkali trialkyl aluminum hydride is converted into aluminum alkali and tetra-alkyl. These complex compounds are much more stable to Al(CH2CH2. CH2. C3)3 heat than is aluminum hydride, and can readily be freed aluminum diethylbutyl, aluminum ethyl dibutyl and from all traces of ether by evaporating the solvent and 80 aluminum tributyl, can be formed successively from heating in vacuo to temperatures of 100 to 120° C. If ethylene and aluminum tri-ethyl in just the same way as they are then dissolved or suspended in a non-ethereal aluminum tri-ethyl is finally formed from aluminum solvent, such as hexane or another saturated aliphatic hydride and ethylene via two intermediate stages. hydrocarbon, they can be reacted in this solvent with The feature which is completely analogous in both 4 mol of aluminum halide, whereupon the following processes is the conversion in each case of an aluminum reaction takes place: AAlH4--/3 AIXs=1%AlR3--AX compound of relatively low molecular weight into an (A=alkali metal, X-halogen). This process can also aluminum compound of higher molecular weight by the serve to convert into ether-free aluminum trialkyls, aluminum trialkyl etherates, which have been produced addition of an olefin. This addition takes place more in a manner different from the herein-described process 70 slowly than the addition of aluminum compounds con of the invention, for example, from aluminum magnesium taining hydrogen, and consequently in the case of react alloys and alkyl halides in ether. This possibility is ing aluminum hydride with ethylene, the al-H group is specifically mentioned here because the addition of the first converted and only then are the substituents built olefin to the complex alkali aluminum trialkyl hydride up from ethyl to butyl, etc. This process is preferably takes place according to the process of the invention, and carried out at rather higher temperatures than in the 2,826,598 5 6 case of hydrogen-containing aluminum compounds. A addition reactions take place very successfully with vinyl temperature of 100 to 140° C. has proven advantageous. cyclo-hexene, when it is principally the vinyl group It is obvious that when ethylene is added to aluminum tri-ethyl, it is not possible to carry out the individual stages of building up the final compound in a manner sharply distinguished one from the other, since the proc which reacts. Olefins with an intermediate double bond, esses shown on paper as taking place successively, also such, for example, as butene-(2) or cyclohexene, are proceed concurrently, so that in a reaction mixture of less reactive and require long reaction periods, unless the this kind, after one mol of ethylene has been absorbed, double bond is distinguished by increased activity, as in aluminum dibutyl ethyl can already be detected, besides 0 the case of dicyclopentadiene, the aluminum butyl di-ethyl, which is mainly formed, so that a corresponding proportion of aluminum tri-ethyl still remains unchanged. It is also obvious that the re CH activity of the al-C group, which makes possible the addi CB tion of olefins, cannot be independent of the residue at 5 tached to al, for instance, aluminum tributyl, under the the left-hand bond of which as shown above adds on above-indicated conditions, i. e., at 100 to 40 C., can aluminum trialkyl very readily (and, of course, also give aluminum hexyl dibutyl, aluminum dihexylbutyl, and aluminum hydride, and the like). Aluminum trialkyls aluminum trihexyl. Quite generally, therefore, mixtures are less readily added to isobutylene and in general to 1.1- are formed of aluminum compounds of the formula: 20 dialkylated ethylenes such as (CH). CHis CHg Al-(CEI). CHs C=CH, (CEI). CH C.C. wherein m, n, p represent small whole numbers of up to 25 and the like. If it is desired to build up high molecular about 6, the average value of which is dependent on the weight organo-metallic compounds from these, then it is total quantity of ethylene absorbed by the aluminum tri best to use beryllium dialkyls, which are, of course, much alkyl, and this can be controlled in a simple way by more valuable than the aluminum compounds, and in observing the reduction in the pressure of the ethylene general react quite similarly to the aluminum trialkyls, which is preferably employed in the compressed state. 30 but are added very readily to 1.1-dialkylated olefins, for It also depends, of course, on the reaction period. example When the experimental temperature is increased above CH CEig about 140° C., the velocity with which ethylene is taken up is certainly very high, but decomposition simultane C=CH -- Be(CH), a -CH-Be-C.H. ously takes place as well to an increasing degree, and to 35 CBIs CBs, C2H an increasing degree reaction products are formed which A priori all the aluminum and beryllium compounds here are no longer aluminum trialkyls. In order to carry out mentioned could be added in two different directions to the process of the invention successfully, it is, therefore, all unsymmetrical olefins. It has been found that the essential to keep the experimental conditions and the addition products always contain the metal atoms on the quantitative course of the reaction well under control, 40 carbon atom which is richest in hydrogen, i. e., alpha which can be done on the one hand by not allowing the olefins always form practically exclusively products with temperature to rise too far above the temperature. Zone the metal on the CH- group, for example, in which the reactions begin to proceed at all at a per ceptible speed, and by choosing as the upper temperature C C.H. limit substantially the temperature which permits of CH-CH=CH, +HAl - C-C-CH-Al velocities which are still utilizable on a technical scale. CHs CH This upper limit is approximately 140 C. in the case of the reaction of ethylene with aluminum triethyl; it varies CEg CE from case to case, but can in any particular case be determined readily by one skilled in the art by a few 50 3 CHsX-OH, -- an CH on-en s preliminary experiments. For the synthesis of aluminum trialkyls from aluminum hydride, it is approximately 80 (CEI):Al-3CH3.C.C.C.H.C-CHart C. so long as unchanged hydride is still present, and in the case of the addition of alkyl aluminum hydrogen com emotion.orget-C4 3Al pounds, it is higher at 100 to 120° C. In this case also, 55 The organic aluminum and beryllium compounds, however, it is unwise to exceed the limit of 100° C. when which can be obtained in great numbers and with great it is desired to stop the reaction at the stage of addition possibilities of variation by the above-described processes, exclusively to all the al-H group. are primarily of importance as polymerization catalysts It lies in the nature of the present invention that the for olefins. They also have a considerable interest as in same substances can occur either as starting materials 60 termediate products for further reactions. Some of their or as end products, i. e., as products of the process. applications are mentioned here. Decomposition with Thus, ethylene can be added to aluminum tripropyl pro water, dilute acids or the like, liberates the organic sub duced in conventional manner, thus converting it mainly stances in the form of hydrocarbons: into Al(CH)3. On the other hand, the same aluminum tripropyl can also be the product of the process, when, 65 for example, aluminum trimethyl is combined with eth Insofar as the aluminum alkyls or alkali aluminum ylene, or aluminum hydride is combined with propylene. tetraalkyls have been produced from olefins by addition The addition of aluminum trialkyls to olefins takes of AlHs, LiAlH4 or the like, the successive reactions rep place particularly smoothly and readily in the case of resent a hydrogenation of the olefin. Of course, there ethylene itself, and also in the case of all mono-alkyl 70 are simpler methods of hydrogenation, and normally these substituted ethylenes (alpha olefins). In this case the new possibilities of hydrogenating olefins opened up by nature of the substituted product has comparatively little the reactions here described will not be used. On the effect. The latter must only not contain components other hand, these new possibilities may be used with ad which react with the sensitive aluminum compounds to vantage in the selective hydrogenation of certain types of decompose them, Thus, for example, the above-described 5 olefins (for example, Re-CH=CH and R'C=CHg) in y

2,826,598 a 7 8 mixtures with other less reactive olefins or for the partial characteristic of the reactants for the Grignard com hydrogenation of di-olefins with two different types of pounds. double bonds. Examples of this are the conversion of While the addition products of the invention are ob vinyl cyclohexene viously of importance for the synthesis of hydrocarbons, their role is in no way limited to this. Decomposition of the products of the process with halogens-iodine, { D-CH=CH, bromine, chlorine-leads, for example, to halogeno-par into ethylene cyclohexene affins, and it is worthy of note that the following reac tion can, for example, be carried out in this way: {D-CH-CH, 10 CEIg CEg and of Yc-CH, + alE- CH-CH-al+ bi, CE cCHs (al-one-third Al) 5 CH CH-C.Br. --Brial into cit? of6T). i. e., in this way it is possible to add HBr indirectly to CH2 20 the olefin in a direction opposite to the direction of the El direct addition, which always goes to CB Co In this connection it should be mentioned that one double N bond in the fulvenes, for example, dimethyl fulvene, re C-CH3 acts very readily with the group al-H (al-/3A1) so 25 that by decomposing with water addition products pro The so-called peroxide effect for the abnormal addition duced according to the invention dihydrofulvenes are ob of hydrogen bromide does not take place in the case of tained of a constitution not yet further known. this type of olefin. In the case of valuable and sensitive olefins and di From the organic beryllium compound with a quater and poly-olefins, in order to ensure as smooth as possible 30 nary carbon atom mentioned further above, the bromide a partial hydrogenation, it has proven advantageous first to produce the addition products according to the inven C4Ig tion with CH3. AlH2 or (C2H5)2AlH, since the addition -chip r of these often takes place more smoothly than that of C2H, CH5 AlH or LiAlH4. The decomposition of the addition 35 products then leads both to the formation of partially can be obtained, which is only difficulty accessible in hydrogenated substances containing a plurality of un other ways, or with carbon dioxide the acid saturated bonds and also to the evolution of methane or ethane, which has no disadvantages, however, apart from Yo-ch.c OOH an only partial utilization of the aluminum atoms for 40 / the hydrogenations. CEs, C2H5 Insofar as the addition products of the invention have can be produced. Finally, reference may here be made been produced from aluminum or beryllium alkyls and to the conversion of the addition products of the inven olefins, decomposition with water gives products in which tion with mercury or cadmium or zinc dihalides, which it appears from the formula that hydrogen and alkyl follows the equations: AllR3-3HgCl2=AlCl3+-3Cl.Hg.R; have been added to the double bond of the olefin, for AIR-3CdCl2=AlCl3-3Cl.Cd.R; example, al. C. CH2CH2. Cha-CEE3 (CH2)9.C-ECEI2 = and gives compounds, of which those of mercury are dis CHCH.) H.CH at -> CH3(CH2)g. (H. CH 50 tinguished by bactericidal and fungicidal properties, whereas those of zinc and cadmium can be used as inter CH C4Ho mediate products for syntheses. They are only accessible CH ; Cig CH in wide range of different constituents via the Substances N N of the invention as intermediate products. C=CH+be C.H.- (-CH be Hm--3 G-CH, This enumeration of the various valuable uses of the CBs C25 &H, C2H5 C2Es 55 products of the process of the invention is not in any Special reference may be made to the simple synthesis way complete. of hydrocarbons with quaternary carbon atoms by means The following examples are given to illustrate the in of beryllium alkyls in accordance with the second equa vention and not to limit the same: tion. To this extent, therefore, the addition products of the invention provide possibilities of synthesis susceptible 60 EXAMPLE 1. of great variation of unitary hydrocarbons of predeter A. luminum triisobutyl from aluminum hydride and isobu mined structure. Since the compound tylene, AlH -- 3 (CH ) CFCHFAl (CHCH ( CH ) 2 ) 3 30 g. of aluminum hydride of 65% strength, con used in the reaction shown by the first of the last two 65 taining ether, such as can be obtained by evaporating equations above can be produced from alpha-butylene an ethereal solution of aluminum hydride and subse and AlH, the reaction makes possible the synthesis of quently heating in vacuum and high vacuum to 60 to the hydrocarbon 70° C., are introduced in an atmosphere of nitrogen into a 500-cc. autoclave and 200 g. of completely dry CHCH.) H.CH, 70 isobutylene are forced in. The autoclave is heated with CEto shaking. The reaction begins at 60 to 65° C. and is from alpha-butylene and alpha-dodecylene. complete after six to eight hours. After blowing off These possibilities are reminiscent of the Grignard re excess isobutylene, the liquid crude product is forced action, but no substances with C=O, C-N, or the like in an atmosphere of nitrogen into a distilling flask and groups are required as starting materials, such as are is distilled in vacuo. Two clearly distinguished fractions 2,826,598, 9 10 are thus obtained. . Aluminum triisobutyl Al(i-CH)3 and thereafter stirring and warming gently. After filtera distils over at 33 to 35°C. under 0.1 to 0.15 mm. Hg ing off and centrifuging off the lithium chloride, the pressure and solidifies in a collecting vessel cooled with hexane is distilled off and the residue is subjected to a ice to form long colorless needies. If the vacuum is short-path distillation in a very high vacuum. At a bath increased, aluminum triisobutyl etherate distils over at temperature of 120° C., a colorless liquid passes over: 58 to 59° C. at 10-8 mm. pressure as a colorless liquid. Calc.: A 9.57%. Found: A 9.782%. The yield consists of 64 g. Al(i-C4H9)3 and 51 g. Lithium aluminum tetraoctyl can be obtained in an Al(i-CH) etherate, i.e. a total of 81% of the theo analogous manner, from octene-(1), but this can be retical yield. boiled in an open vessel under reflux (and in an atmos Fraction I contains 13.70% Al, calc. for Al(CH3)3 0. phere of nitrogen) (B.P. 110 to 120° C.). 13.65% A. EXAMPLE 4 Fraction II contains 10.65% Al, calc.for Sodium aluminum tetrapropyl from sodium aluminum Al(CH)3% (C2H5)2O tripropyl hydride and propylene, 10.65% A1. 15: CH--NaAlH(CH) =NaAl (CH ) 4. Both fractions, when decomposed with water or alcohols, 153 g of aluminum tri-n-propyl are dissolved in 500 yield only isobutane (fraction II yields ether also) and cc. of dry air-free hexane, and a fine suspension of 24 g. no hydrogen. of sodium hydride in 150 cc. of hexane is then added in EXAMPLE 2 20 an atmosphere of nitrogen. The hydride dissolves and Aluminum dibutyl hydride from aluminum hydride and the solution heats up by itself. Finally, the solution is heated for some time to 50 to 60° C. The solution is butene-(1), then introduced into a suitable autoclave, 50 to 60 g of propylene are forced in, and the autoclave is heated 410 cc. of an ethereal 0.31 molar aluminum hydride for twenty-four hours to 150° C. After cooling, the solution are forced in an atmosphere of nitrogen into 25 excess propylene is let off and the almost clear solu an autoclave and 14 g. of butene-(1) are condensed tion is forced out with nitrogen. After removal of the with them. Over a period of fourteen hours, the auto hexane from the clear solution, 145 g. of an oily residue clave is brought to a temperature of 70 to 75° C.; ex remain, which crystallize slowly. cess gas is then let off, and the ether is distilled off in NaAl(CH): Calc., Na 10.4; Al. 12.2. Found, Na an atmosphere of nitrogen after the contents of the 30 10.3; Al 11.8. autoclave have been introduced into a glass flask. The The product on decomposition with ethyl hexanol gives residue boils in a high vacuum at 64-66 C. (108 mm.). only propane, but no hydrogen. The product can be Yield: 9.5 g., i.e., 61% of the theoretical. converted into aluminum tripropyl in a manner analogous Analysis: '19.2% Al found; 19.0% Al calculated for to that described in Example 3. Al(CH3)2H. 35 When the product is decomposed-preferably with a EXAMPLE 5 high boiling alcohol, for example 2-ethyl hexanol, to Aluminum diethyl sec.-amyl by addition of aluminum render more gentle the otherwise very stormy reaction diethyl hydride to pentene-(2) 450 cc. of gas (measured at 0° C. and 760 mm. Hg pressure) are obtained per gram of Substance employed 40 (CH3)2AlH.-- CH.CH:CH.CH-CH=CH.G.H.C.H.CH, CH, instead of the calculated 472 cc. The gas consists Arch), exactly of one-third hydrogen and two-thirds n-butane. 36 g. of dry air-free pentene-(2) are introduced to gether with 17.6 g. of Al(CH5)2H in an atmosphere of EXAMPLE 3 nitrogen into a glass ampoule of approximately 150 cc. 45 volume and the ampoule is then fused to seal it. The Lithiumhydride aluminum and alpha-hexene, tri-n-hexyl from lithium aluminum ampoule is then heated (preferably in an autoclave filled with pentane) for six days to 70° C. After cooling, LiAlH4-4CH2:CH. (CH2)3CHFLiAl(CH3)3 the ampoule is opened and the excess pentene-(2) 3 g. of lithium aluminum hydride as free from ether (23.0 g) is distilled off. The residue weighs 31 g, and of as high a strength as possible are heated for 50 i.e., shows an increase in weight of 13.4 g. instead of five hours to 110° C. in a suitable autoclave in an atmos 14 g. The distillation residue is distilled in a high vac phere of nitrogen with 45 cc. of hexene-(1) or with a uum. B. P. 43 to 45° C. (10-8 mm. Hg), d20=0.850. correspondingly greater quantity of a hexene mixture Yield: (excluding a small first running of (CH)AlH) containing hexene-(1), which mixture may also contain 24 g. (H5C2)2Al(CH), i.e. 75% of the theoretical, other hydrocarbons, especially saturated hydrocarbons, 55 Analysis: (a) Found: 17.45% Al. Calc.: 17.30% A. for example, hexane. The autoclave is then filled with On decomposition with ethylhexanol, the product a pasty mass which is stirred after cooling with hexane yields the correct quantity of ethane (2 mols) besides in an atmosphere of nitrogen, and transferred to a pentane, but no hydrogen. glass flask from which the hexane is then distilled off, The aluminum diethyl hydride required for this ex finally in a high vacuum at 60° C. There remain behind 60 periment is preferably obtained by treating an ethereal barely 30 g. (theoretical yield 30.6 g.)-the exact quan solution of diethyl aluminum chloride (CH)AlCl with tity depends on the degree of purity of the lithium alu finely powdered lithium hydride, filtering, distilling off minum hydride employed-of a solid salt-like, white the ether and subjecting the residue to distillation in a residue of the composition LiAl(CH3)4, for example, high vacuum. It is a colorless spontaneously inflam Found: Al 7.22%, Li 1.87%. , Calc.: Al 7.8%, Li mable liquid of B. P. 55 to 56° C./10-3 mm. Hg pres 1.95%. sure, d0=0.8081, n29-147396. On decomposition, with water, or better, with ethyl hexanol, practically no gas is liberated, in particular no EXAMPLE 6 hydrogen. Addition of aluminum diethylhydride to dicyclopentadiene The compound can be converted very readily into pure 70 aluminum trihexyl by suspending it in dry hexane in an atmosphere of nitrogen, adding finely powdered alumi num-chloride in a quantity corresponding to the equation 5 ... CE,..., 2,826,698. 2 4.9 g : of aluminum diethyl hydride with 13.85 g. of and the procedure was again repeated. After six hours. dicyclopentadiene: are sealed in a glass flask by fusing it, in all, 40 g. of ethylene were taken up in this way, and and heated for seven hours to 65° C. After cooling, the: the contents of the autoclave consisted of 90 cc. of a. neck of the ampoule is opened in an atmosphere of very. clear. colorless liquid from which 17 cc. were distilled pure nitrogen and a sample is decomposed with ethyl offin a high vacuum at a bath temperature rising to 130 hexanol. The gas evolved no longer contains, hydrogen. C.. On decomposition with water, the product gave mix After removal of the excess dicyclopentadiene in a high tures of ethane and butane, i. e., consisted of mixtures vacuum, a viscous oily, residue is obtained, which con of aluminum trialkyls Al(CH2--1)3 where n=2 and 4. sists substantially of the addition product of dicyclopenta Methanol was added cautiously with cooling to the diene and diethyl aluminum hydride of the formula given O residue, which contained the higher aluminum compounds, above. On decomposing this compound with water, the whereupon 50 cc. of liquid hydrocarbons were obtained known dihydrocyclopentadiene is obtained: in addition to 3.9 liters of gas. The gas consisted of 90% butane and 10% ethane. off, On distillation with an analytical rotary band column, CH 5. the liquid gave cFL CH 12 cc, n-hexane, B. P. 69 C./760 mm. 13.5 cc.n-octane, B. P. 125 C./760 mm. EXAMPLE 7 9.0 cc. n-decane, B. P. 76 C./26 mm. Partial reduction of dimethyl fulvene 20. 4.2 cc dodecane, B. P. 110° C./26 mm. 1.9 g, of lithium aluminum hydride are dissolved in 3.6 cc. residue ether, and 5.3.g. of dimethyl fulvene are added drop by All the odd number hydrocarbons from pentane to drop. Even at room temperature, the reaction begins undecane and n-tridecane can be obtained in a compara with spontaneous heating up and the color becomes light ble experiment starting from aluminum tripropyl er. Finally, the reaction becomes colorless, and a white, cheesy mass deposits. Aluminum diethyl hydride shows 25. EXAMPLE 11 a similar reaction when dimethyl fulvene is added to it Mixture of aluminum alkyls and HgCl2 in a molecular propertion of 1:1. The reaction in this 10 cc. (0.07 mol.) Al(CH5)3 were introduced in an case can be detected by the great increase in viscosity. atmosphere of nitrogen together with 30 g. of ethylene If 5 N HCl is added with ice-cooling to the product 30 into an 0.2 liter autoclave and heated for ten hours to . obtained in either of these ways, an oil separates, which 110 to 115° C. The reaction mixture was then allowed is of a much lighter color than dimethyl fulvene, and to cool and the excess ethylene was blown off in the boils at 28° C. (11 mm.). It has the composition of an cold. 18 g. of ethylene were taken up. 100 cc. of dry isopropylcyclopentadiene (dihydrodimethylfulvene). air-free cyclohexane were then added to the contents of CH: Calc., C 88.8; H 11:2. Found, C 88.4; H 35 the autoclave and heated to bring about solution, and the 11.1, solution was then forced out of the autoclave with nitror EXAMPLE 8 gen. This solution was added drop by drop over a period Aluminum diethyl hydride and butadiene of 30 minutes to a stirred suspension of 59.5 g. HgCla. 5.7 g. of aluminum- diethyl hydride are heated in an and 145 cc. of cyclohexane and the mixture was then atmosphere of nitrogen to 90 to 95 C., and for a period heated for a further hour to 80° C. The compound pre of sixteen hours a stream of butadiene is passed through cipitated was filtered off with suction and then fused. at a rate of 2 to 3 g. per hour, which leads to the absorp with 1% hydrochloric acid on the water bath, them washed tion of a part only of the butadiene. After cooling, the repeatedly with water, and after drying, recrystallized dissolved, butadiene is first driven off and the residue is from butanol. then distilled in a high vacuum. A distillate is obtained 4.5 A solid, salt-like, white product. was obtained of the containing approximately 19% Al instead of 19.3%, type H(C2H4)HgCl, where n=4-5, and a mercury, con which is the calculated quantity for (HCA) Al(C2H5) tent of approximately 50 to 55% and a chlorine content and also a non-distillable residue which gives both ethane of 9 to 10%. and butane on decomposition with water and consists EXAMPLE 12. mainly of Aluminum triethlyl and octene-(1) (CH2)2Al..CH2CH2CH2CH2Al(CH2)2 14.5 cc. of octene-(1) and 12.5 cc. of aluminum triethyl EXAMPLE.9, were heated in an autoclave in an atmosphere of nitro gen for sixteen hours to 132 C., the autoclave was then Addition of aluminum diethyl hydride to styrene 55. cooled, the contents were then emptied out in an atmos 7.3 g of aluminum diethyl hydride are mixed in a phere of nitrogen, and heated in vacuo (12 mm.) to a glass ampoule, with 8.9 g, of styrene distilled over sodium, maximum temperature of 135 C., whereupon approxi the ampoule is sealed by fusing it, and the reaction mix mately 5 cc, distilled over. ture is heated for twenty-four hours to 65 C. A con In order to elucidate the nature of the reaction product traction of volume of 8.4%. takes place, and the mixture 80 produced, methanol and thereafter dilute hydrochloric becomes viscous. The fact that the viscous product on acid were added to the distillation residue with cooling, decomposition with water, yields only ethyl benzene be-, whereupon 11 cc. of a colorless, oil, were obtained. This sides, ethane,...shows that, the product does not contain a gave, after a first running of a hydrocarbon of the C. styrene polymer, but really contains an addition product series, 5.5 cc. of the hydrocarbon of the type. 65 CH5.CH-CH Al(CH5) OH,-(CH)-H-CH,Cas EXAMPLE 10. which can only have been produced from a compound Addition of ethylene to aluminum triethyl containing the group 30 cc. of aluminum triethyl (0.22 mol.) were: intro duced in an atmosphere of nitrogen into a 200 cc. auto clave together with ethylene under a pressures of 60 at CH-CH)-H-CH-AKCss mospheres and heated to 120 to 125 C. When the pres The hydrocarbon shows the following characteristics: sure had fallen to about 20 atmospheres, more ethylene n20= 1.4.132. B. P. 760-165 C. was forced in to increase the pressure to 90 atmospheres It does not solidify until it reaches a temperature of 2,826,598. 13 14 -80° C. n-Decane boils at a temperature of approxi 12. The improvement according to claim 1, in which mately 10° C. higher and has a melting point of -30 C. said olefinic hydrocarbon is an aralkylene. ... EXAMPLE 13 13. The improvement according to claim 1, in which said olefinic hydrocarbon is a hydro-aralkylene. -- Addition of beryllium diethyl to 2-methyl-pentene-(1) 14. The improvement according to claim 1, in which 2.6 g. (0.039 mol.)=3.5 cc. of beryllium diethyl and said olefinic hydrocarbon is an isocyclic hydrocarbon 11.5 g. (0.137 mol.) =17 cc. of 2 methyl-pentene-(1), with at least one double bond. .. 15. In the production of organo aluminum compounds C.H...-CH, the improvement which comprises heating an aluminum Ca 0 hydride with an olefinic, hydrocarbon, having the vinyl are sealed in a glass ampcule by fusing it and heated for idene radical eighty-two hours to 100° C. The course of the reaction can be followed by observing the contraction of the mix (-ch, - ture. This amounts to 0.43 cc. in all, and remains con stant after the above-quoted period. to a temperature below the temperature of decomposition Aliquot parts of the mixture, when cautiously decom aid secondary changes of the reactants and for a period posed with 2-ethylhexanol, liberate exactly half the quan of time sufficient to obtain addition products containing tity of ethane which would be obtained from unchanged the olefinic hydrocarbons in whole number stoichiometric beryllium diethyl. The reaction proportions of 1 to 6 per metal equivalent, and recovering 20 the addition compound of the reactants. CH CH - 16. The improvement according to claim 15 in which C=CH -- Be(CH) - said olefinic hydrocarbon is a non-symmetrical one carry CH CHCHC-H. Bec-H. ing different hydrocarbon substituents at said radical. has clearly taken place. This is confirmed by the fact 17. The improvement according to claim 15 in which that, on distilling off the excess methylpentene on a boil 25 said heating is effected at a temperature of about 50-120° ing water bath, finally in a weak vacuum, 5.9 g, of a resi C. until three mols of said olefinic hydrocarbon are added, due remain, which corresponds exactly to 0.039 mol. of the mixture being cooled and an aluminum trialkyl re this addition product. covered. We claim: 18. The improvement according to claim 17 in which 1. In the production of organic compounds of alumi 30 said aluminum hydride is solid aluminum hydride and in which the addition compound is recovered by removing . num and beryllium the improvement which comprises unreacted olefinic hydrocarbon from the reaction mixture heating with an olefinic hydrocarbon having at least one and subjecting the same to distillation. unsaturated bond a metal compound having the grouping 19. The improvement according to claim 15 in which Me(R) 35 said metal compound is an ether containing aluminum in which Me is a metal selected from the group consist hydride, and in which aluminum trialkyl etherate is re ing of aluminum and beryllium, R is at least one member covered by evaporating solveit and remaining unreacted including the same and different members selected from olefin after the heating and by distillation. the group consisting of hydrogen, aliphatic radicals, aro 20. The improvement in accordance with claim 15 in matic radicals and combinations thereof including aralkyl 40 i. which said olefinic hydrocarbon is one corresponding to and cycloalkyl radicals, and n is the valence of the metal the general formula Me, said heating being effected to a temperature below the temperature of decomposition and secondary changes X. of the reactants for a period of time sufficient to obtain C-CI addition products containing the olefinic hydrocarbons X in whole number stoichiometric proportions of 1 to 6 for which X is an aromatic hydrocarbon radical and for per metal equivalent, and recovering the addition com which X is one member selected from the group con pound of the reactants. sisting of hydrogen and aromatic hydrocarbon radicals. 2. The improvement according to claim 1 in which said 21. The improvement according to claim 15 in which metal compound is present in the form of a molecule 50 said olefinic hydrocarbon is one corresponding to the compound with an ether. general formula 3. The improvement according to claim 1 in which said metal compound is present in the form of a complex compound with an alkali metal hydride. C=CH 4. The improvement according to claim 1 in which said 55 y metal compound is present in the form of a complex for which y is a non-aromatic isocyclic six-membered ring compound with an alkali metal alkyl. hydrocarbon radical and for which y is one member 5. The improvement according to claim 1 in which said selected from the group consisting of hydrogen and non metal compound is present in the form of a complex aromatic isocyclic radicals. compound with an alkali metal aryl. 60 22. The improvement according to claim 15 in which 6. The improvement according to claim 1 in which said olefinic hydrocarbon is one corresponding to the said heating and contacting is effected in the presence of general formula an organic solvent. 2. 7. The improvement according to claim 6, in which N said solvent is an ether. 65 CeCE 8. The improvement according to claim 1, in which 2. said heating is effected under pressure. for which z and z is at least one member selected from 9. The improvement according to claim 1, in which the group consisting of hydroger and saturated aliphatic said olefinic hydrocarbon is an aliphatic olefin with an hydrocarbon radicals, and in which said heating is effected end positioned double bond. 70 under pressure. 10. The improvement according to claim 9, in which 23. The improvement according to claim 22 in which said olefin is ethylene. z and z are dissimilar saturated aliphatic radicals. 11. The improvement according to claim 1, in which 24. The improvement according to claim 1 in which said olefinic hydrocarbon is an aliphatic olefin with at said metal compound is a solid aluminum hydride which least two double bonds. 5 has been freed from ether prior to said heating by boiling p

2,826,598 15 6 withs an indifferent solvent, with continuous withdrawal dialkyl with a non-symmetrical olefinic hydrocarbon of the and replacement of the distillate: general formula. 25. The improvement according to claim 24 in which said indifferent solvent is selected from the group consist Yo-ch, ing of saturated and aromatic hydrocarbons having a 5 / boiling range of about 40-80 C. at a. pressures not in 2 excess of normal. for which z and z1 are dissimilar saturated aliphatic 26. The improvement according to claim, 1 in which radicals. said metal compound is aluminum hydride, in which said 30. The improvement according to claim 1 in which heating is effected at a temperature of about 50-120° C. 10 said metal compound is diethyl aluminum hydride, said until from 1 to 2 mols of said olefin are added to each olefinic hydrocarbonethylene and said addition compound mol of aluminum present, in which the reaction mixture of the reactants...aluminum triethyl. is thereafter cooled and subjected to distillation and in 31. The improvement according to claim 1 in which which a substituted aluminum hydride is recovered hav said metal compound is an ethyl aluminum hydride, said. ing the general formula 15 olefinic hydrocarbon ethylene and said addition com B pound of the: reactants aluminum triethyl. A14R, References Cited in the file of this patent YR UNITED STATES PATENTS. 20 in which R' is a hydrocarbon radical andR is a member 2,052,889 Loder et al. ------Sept. 1, 1936 selected from the group consisting of hydrogen:and hydro 2,221,000; Kventzel et al. ------Nov. 12, 1940 carbon radicals. 2,229,661 Mann ------Jan. 28, 1941 27. The improvement according: to claim li in which 2,263,666 Wilson ------Nov. 25, 1941 said metal compound is a substituted aluminum hydride. 2,299,716 Van Peski------Oct. 20, 1942 having the general formula. 2,385,543 Ross et al. ------Sept. 25, 1945 H. 2,413,531, Verbanc ------Dec. 31, 1946 / 2,421,090 Smith et al. ------May 27, 1947 Al-R 2,510,765 Stewart ------June 6, 1950 Y. 30 2,567,972 Schlesinger et al. ------Sept. 18, 1951 in which R is a hydrocarbon radical and R' is a mem. 2,579,251 Coates et al. ------Dec. 18, 1951 ber selected from the group consisting of hydrogen and 2,786,860 Ziegler et al.------May 13, 1952 hydrocarbon radicals. OTHER REFERENCES 28. In the production of organo aluminum compounds Finholt et al.: J. Am. Chem. Soc., vol. 69, pages 1199 the improvement, which comprises heating an aluminum 35 1203, (1947). trialkyl at a temperature of about 50-120° C. with an Nystrom et al.; J. Am. Chem, Soc., vol. 69, pages 1197.- olefinic hydrocarbon having the terminal radical 1999, (1947). Trevoy et al.: J. Am. Chem. Soc., vol. 71, pages 1675 1678, (May 1949). (=CH, 40 Sidgwick: Chemical Elements and Their Compounds, for a period of time sufficient to obtain addition products vol. I, page 414, Oxford Univ. Press, London (1950). containing the olefinic hydrocarbons in whole number Schechter et al.: Boron Hydrides and Related Com stoichiometric proportions of 1 to 6 per metal equivalent, pounds, page 29, prepared for Dept. of Navy, Bureau of and recovering the addition compound of the reactants. 45 Aeronautics by Callery Chemical Co. (March 1951). 29. In the production of organo, beryllium compounds; Hurd: Chemistry of the Hydrides, page 87, New York, the improvement which comprises: heating a beryllium John Wiley & Sons, Inc., (June 1952). UNITED STATES PATENT OFFICE Certificate of Correction Patent No. 2,826,598 March 11, 1958 Karl Ziegler et al. It is hereby certified that error appears in the printed specification of the above numbered patent requiring correction and that the said Letters Patent should read as corrected below. Column 1, line 57, for "of beryllium read -or beryllium-; column 2, line 5, for “everal’ read -Several-; column 5, line 58, for “group’ read groups-; column 14, lines 42 to 45, the formula should appear as shown below instead as as in the patent X Yo-CH, Xi Signed and sealed this 20th day of May 1958.

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Attest: KARL. H. AXLINE, ROBERT C. WATSON, Attesting Officer. Commissioner of Patents.