3,294,827 United States Patent Office Patented Dec. 27, 1966 1. 2 3,294,827 which will remain inert during the preparative procedure. QUATERNARY AMMONIUMMETAL COMPOUNDS The term "capryly' used herein refers to the hydrocarbon Ronald R. Swanson, Minneapolis, Minn., assignor to radicals (octyl and decyl) derived from a mixture of General Mills, Inc., a corporation of Delaware caprylic acid and capric acid. No Drawing. Filed Sept. 26, 1961, Ser. No. 140,691 Another method for preparing the compounds of the 12 Claims. (CI. 260-429) present invention is by contacting the quaternary ammo nium starting material with a simple metallic salt. The This invention relates to novel quaternary ammonium quaternary and the metal salt are combined in a mutual compounds. solvent and, upon removing the solvent, the desired qua It is an object of this invention to provide novel qua 10 ternary ammonium metal compound is prepared. For ternary ammonium metal compounds. It is another ob example, if it is desired to prepare a quaternary ammo ject of this invention to provide the novel process for nium compound having an anion MnCl4, this can be the preparation of quaternary ammonium metal com done by contacting quaternary ammonium starting mate pounds. Other objects will appear hereinafter. rial with manganese chloride in a mutual solvent such as The objects of this invention are accomplished by a 5 ether or isopropanol. While the product must be com fatty quaternary ammonium metal compound wherein the pletely soluble in the chosen solvent, it is not generally anion of said quaternary compound is an inorganic anion necessary that both the starting quaternary compound and containing a metal of Group VIIB of the Periodic Table. the metallic salt be completely soluble in the solvent, but The compounds of the present invention are represented it is only necessary that they be partially soluble. This by the following formula: 20 technique is most useful when the anion of the quaternary ammonium compound is identical to the anion of the XmY metal compound. For example, the quaternary ammo where X is a fatty quaternary ammonium cation and Y nium chloride should be used to prepare the manganese is an inorganic anion containing a metal of Group VIIB chloride complex from the manganese salt. One advan of the Periodic Table, and m is the valence of the in tage of this technique and a highly unusual feature of organic anion. the present invention is that it is possible to prepare, As used herein, the term "fatty' refers to an aliphatic by this method, anions which could not otherwise be hydrocarbon radical of 8-24 carbon atoms. The term prepared because of their instability in water. "fatty quaternary ammonium” refers to a quaternary am Using the above described preparative procedures, fatty monium compound having at least 1 fatty radical attached 30 quaternary ammonium compounds having the following to the quaternary nitrogen atom. As used herein, the anions can be prepared: MnO, MnO, Mn4O, term "metals of Group VIIB of the Periodic Table' MnO2, MnO, MnO, MnO, Mn43O37, refers to manganese, technetium (masurium) and rheni MnO-6, MnO1-2, MnF-2, Mn(CN)6-5, Mn(CN)6, um, as shown in the Periodic Table set forth on page 573 Mn(CN)63, MnCl2, IMn(C3H2O4)2(H2O)2], of General Inorganic Chemistry by Sneed and Maynard, 35 MnO-2, MnF-2, ReO-1, ReO2, ReCls, ReCls, Van Nostrand, New York, 1942. ReO, ReF-2, Rel, ReSO-1, ReSO-1, ReSO-1, The compounds of the present invention are prepared ReBre-2, Reis, ReOClio, ReCIOH-2 TcO-1. Still by reacting fatty quaternary ammonium compounds, par other compounds containing other anions containing ticularly the fatty quaternary ammonium chlorides, with metals of Group VIIB will be obvious to those skilled in a salt having the desired metal containing anion. Using 40 the art. this procedure, the fatty quaternary ammonium compound In order to illustrate certain preferred embodiments of is dissolved in an organic solvent and contacted with the present invention, the following examples are included. aqueous solution of an inorganic salt having the metal Unless otherwise indicated, all parts and percentages used containing inorganic anion. The aqueous solution is then herein are by weight. discarded and the organic solvent removed from the or 45 ganic phase by distillation, preferably under vacuum, to Example I yield the product of the present invention. - Into 250 ml. of isopropanol was added 19.8 grams of Because of the availability of quaternary ammonium MnCl2.H2O. The material did not completely dissolve. chlorides, they are generally used as a starting material in After one hour of mixing, 99 grams of methyl tricaprylyl the preparation. However, other quaternary ammonium 50 quaternary ammonium chloride was added, at which time salts can be used with equal Success. Suitable quaternary the previously undissolved manganese dichloride was ammonium compounds for the preparation of the com rapidly dissolved. The isopropanol was then removed pounds for the present invention include trimethyl octyl under vacuum to leave a compound of the formula ammonium chloride, methyl triisooctyl ammonium chlo ride, dimethyl dioleyl ammonium chloride, monomethyl 55 (RNCH ) 2MnCl4 trioleyl ammonium chloride, tetrapalmityl ammonium where R is caprylyl. The product analyzed 4.85% man chloride, trimethyl myristyi ammonium chloride, dimethyl ganese, 13.3% chlorine and 2.65% nitrogen as compared distearyl ammonium chloride, trimethyl tallow ammo theoretical values of 4.92%, 12.7%, and 2.51%, nium chloride, dimethyl dicoco ammonium chloride, respectively. wherein "coco” refers to fatty radicals derived from coco 60 Example II nut oil fatty acids, methyl octyl morpholium chloride, di To 500 ml. of methanol were added 37.7 g of MnSO, laury morpholium chloride, lauryl Stearyl morpholium 24.5 g. of NaCN and 486 g. of methyl tricaprylyl am chloride, octyl pyridinium chloride, stearyl pyridinium monium cyanide. After filtering, the solvent was evapo chloride, methyl trilinoleyl ammonium chloride, trioctyl rated under vacuum. The residue was dissolved in ben benzyl ammonium chloride, stearyl tribenzyl ammonium 65 chloride, and butyl lauryl dibenzyl ammonium chloride. zene, filtered and stripped of solvent under vacuum. The quaternary ammonium compound can be saturated, There was obtained a dark viscous liquid product having or contain ethylenic, acetylenic, or aromatic unsaturation. the structural formula (RNCH3)Mn(CN)6. Generally, the quaternary ammonium compound may con Example III tain other functional groups, although it is generally pre 70 To 2.73 g of NaReO, in ether were added 5.86 g. of ferred to employ compounds containing functional groups dimethyl distearyl ammonium chloride. After filtering 3,294,827 3. 4. the solvent was evaporated to yield light yellow solid nitrogen atom is an aliphatic hydrocarbon radical of product of the formula R2N (CH3)2ReO4 where R is 8-24 carbon atoms. Steary. 6. Complex compounds of the formula: Example IV (RNCH ) 2MnCl4 To 172.5 g. of NaMnO4·10H2O in 500 ml. of methanol 5 Were added 420 g. of trimethyl caprylyl ammonium chlo where R is selected from the group consisting of octyl ride. After filtering and evaporating the solvent, the and decyl. residue was recrystallized from dimethyl formamide. 7. Complex compounds of the formula: There was obtained a dark brownish green solid product XMn (CN) 6 of the formula (RN(CH3))MnO, where R is caprylyl. O where X is a fatty quaternary ammonium cation wherein The foregoing examples are illustrations of certain at least one of the four organic groups attached to the preferred embodiments of the present invention and are nitrogen atom is an aliphatic hydrocarbon group of 8-24 not to be construed as limitations on the scope thereof. The compounds of the present invention are useful as carbon atoms. sizing materials for papers, cellulosic materials, poly 8. Complex compounds of the formula: amides, glass, vitreous and ceramic compositions, as fungicides, as pesticides, as biocides, as bactericides, as where R is selected from the group consisting of octyl anti-barnacle coatings, as corrosion inhibitors, as dyes, and decyl. as pigments, as colorants, as ultraviolet protectors, as 9. Complex compounds of the formula: wood preservatives, as additives for plastic materials, as 20 additives for adhesives, as additives for glass laminates, XReO4. as an additive for printing inks for plastics, as fuel and where X is a fatty quaternary ammonium cation wherein gasoline additives, as lubricant additives, as coating addi at least one of the four organic groups attached to the tives, as materials of construction for nuclear engineering, 25 nitrogen atom is an aliphatic hydrocarbon group of 8-24 as accelerators for curing of synthetic resins, as catalysts carbon atoms. for emulsion polymerization, as catalysts for intermediate materials for the preparation of catalysts for a variety of 10. The complex compound of the formula: chemical reactions, as additives for vinyl plastisols, as RN (CH ) ReO4. electroplating materials, as a source of pure metals where R is steary. having unusual properties because of their complex na 30 1. Complex compounds of the formula: ture, as vapor-phase plating chemicals, as anti-static addi tives for plastics and coatings, and the like. The products XMnO4. of the present invention can also be used to impregnate where X is a fatty quaternary ammonium cation wherein ceramics, silica, clay, alumina, and the like, and after 35 at least one of the four organic groups attached to the firing the impregnated material, a product is obtained nitrogen atom is an aliphatic hydrocarbon radical of having the desired metal uniformly impregnated through 8-24 carbon atoms. out the material. 52. Complex compounds of the formula: The embodiments of the present invention in which an exclusive property or privilege is claimed, are defined as 40 follows: where R is selected from the group consisting of octyl 1. Complex compounds of the structure and decyl. XY References (Cited by the Examiner where X is a fatty quaternary ammonium cation wherein 45 at least one of the four organic groups attached to the UNITED STATES PATENTS nitrogen atom is an aliphatic hydrocarbon radical of 8-24 2,580,473 1/1952 Sowa et al. ------260-429 carbon atoms, Y is an inorganic anion containing a metal 2,798,103 7/1957 Schaffer et al. ------260-429 of Group VIIB of the Periodic Table of Elements and m 2,902,401 9/1959 Harwood et al. ------260-429 is the valence of said anion. 50 2. The complex compounds of claim 1 wherein the OTHER REFERENCES metal is manganese. 3. The complex compounds of claim 1 wherein the Karrer: Organic Chemistry, 2nd English edition, Else metal is technetium. vier Publishing Co., New York, N.Y., 1946, page 119. 4. The complex compounds of claim 1 wherein the 55 metal is rhenium. HELEN. M. McCARTHY, Acting Primary Examiner. 5. Complex compounds of the formula: ABRAHAM H. WINKELSTEIN, TOBLAS E. LEVOW, Examiners. where X is a fatty quaternary ammonium cation wherein W. J. VAN BALEN, T. L. IAPALUCCI, Assistant at least one of the four organic groups attached to the 60 Examiners.