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United States Patent Office Patented July 30, 1968 2 Solutions Some of Which Have Detergency and Coloring 3,395,171 Properties, and Are Generally Stable

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United States Patent Office Patented July 30, 1968 2 Solutions Some of Which Have Detergency and Coloring 3,395,171 Properties, and Are Generally Stable 3,395,171 United States Patent Office Patented July 30, 1968 2 Solutions some of which have detergency and coloring 3,395,171 properties, and are generally stable. PROCESS FOR PREPARING HEXADECAHEDRAL Derivatives of cup shaped decaboranes have been pre DECABORANE, DERVATIVES AND RESULT pared by reaction with monooxyacycloalkanes in solutions ING PRODUCTS William C. Drinkard, Jr., Wilmington, Del, assignor to of the monooxyacycloalkane. This reaction occurs at very E. I. du Pont de Nemours and Company, Wilmington, slow rates, requiring as long as four weeks for oxolanes Del, a corporation of Delaware and twenty hours for oxetanes at room temperature. No Drawing. Continuation-in-part of application Ser. No. In the present invention a process for preparing deriva 220,909, Aug. 31, 1962. This application June 30, 1965, tives of hexadecahedral decaborane is provided which is Ser. No. 468,565 more rapid and economical than the processes currently 12 Claims. (CI. 260-462) 10 used to make derivatives of cup shaped decaboranes. This process comprises reacting an acid hydrate of hexadeca hedral decaborane (H2BioHo'nH2O with an epoxide ABSTRACT OF THE DISCLOSURE having the structural formula A process for preparing derivatives of hexadecahedral 5 O decaborane by reacting an acid hydrate of hexadecahedral decaborane H2B10H10 inH2O) with an epoxide having the Y-C4 So-Y. structural formula, Y Y It is thought that in this reaction one of the C-O bonds 20 of said epoxide is ruptured and the oxygen atom freed by the ruptured bond attaches to a boron atom of the deca borane. In the epoxide each of Y1, Y2Y and Y is hydro wherein Y1, Y2, Ys and Y are hydrogen or monovalent gen or a monovalent radical. Any epoxide which will react radicals which are either monomeric or polymeric in char with benzene in the presence of aluminum chloride (cat acter. The product is conveniently recovered by precipita 25 alyst) at a temperature less than about 100° C. to form a tion as an insoluble salt; for example, the cesium salt, Substituted benzene of the type Cs2B1H8(OR)2. The hexadecahedral decaborane deriv atives are useful as detergents and as pigments or dyes. -OR 30 This is a continuation-in-part of application Ser. No. where OR corresponds to the epoxide utilized with the 220,909, filed Aug. 31, 1962 and now abandoned. epoxy ring opened is useful in this invention. This invention relates to a process for preparing deriva By conducting the reaction of this invention in a solu tives of hexadecahedral decaborane and to compounds tion of the acid hydrate and regulating the temperature containing a hexadecahedral decaborane structural unit. to provide a controlled reaction rate, high yields of sub Molecules containing ten boron atoms (decaboranes) Stituted hexadecahedral decaborane anions are produced. can be made with two structural arrangements; the re These substituted anions have the formula cently discovered hexadecahedral (16 sides) decaborane BioHa (OR)2)2 anion (BoH14) and the well known cup shaped decabo 40 rane B10H14. A description of the cup shaped decaborane where -OR corresponds to the epoxide utilized with the can be found in Gould, Inorganic Reactions and Struc epoxy ring opened to form a monovalent --OR radical ture 130 (Revised edition 1962, Holt Rinehart and Win which is bonded to a boron in the decaborane through the ston Inc.). The structural arrangement of the hexadeca oxygen. The product is conveniently recovered by pre hedral decaborane anion is analogous to two square-based cipitation as an insoluble salt, for example, the cesium salt pyramids having their bases spaced apart and facing each Cs2B10H8 (OR)2. By varying the relative quantity of other with one base rotated 45° relative to the other; each epoxide employed, other similar anions containing ether corner of each base is a boron atom and each boron atom like functions can be obtained having the general formula is connected by a bond to the two adjacent boron atoms BioHoy (OR)y) where y is a whole number from 1 of its base, the boron atom at the apex of its pyramid and 50 to 4 preferably, and permissibly 5-10 inclusive. the two closest boron atoms of the facing base. A hydro The Substituted decaborane compounds of this inven gen atom is attached externally to each boron in this sym tion can have electrical charges arising from the nature metrical arrangement and the total structure carries an of the R groups in addition to the charge associated with electric charge equivalent to two electrons. the hexadecahedral decaborane. For example, R may bear The similarity between the hexadecahedral and the cup carboxyl groups which, in ionic form, require the presence shaped decaborane molecules ends with the fact that they of a cation. As a further illustration, R may bear basic contain the same number of boron atoms. In addition to groups, e.g., NH2, which will form ionizable salts with the structural differences described above, their elemental acids. Cations and anions derived from R groups are con makeup differs by the presence of four additional hydro sidered to be part of these groups and are included within gens in the cup shaped decaborane molecule. With re 60 the scope of the definition of R. spect to property differences the cup shaped decaborane Solutions of the acid hydrate of hexadecahedral deca decomposes in water to form weak boric acid (pH about borane useful in carrying out the reaction of this invention 5) and derivatives of cup shaped decaborane usually are can be in the form of an aqueous syrup in which water active reducing agents for many metallic ions, do not form and the acid hydrate are present in about equal amounts ions and are generally unstable. In contrast the hexadeca by weight. However, no water is necessary for the present hedral decaborane anion is stable in the presence of acid process beyond that required to permit the hexadecahedral and in combination with hydrogen ions forms a strong decaborane anion to be in its acidic form. acid hydrate having the formula H2B10H10 inH2O (pH In a preferred procedure this aqueous syrup is mixed about 2) and derivatives of hexadecahedral decaborane with a solvent such as glyme (ethylenegylcoldimethylether) by virtue of the presence of the decaborane alone are not 70 to form a solution, and an epoxide in fluid form (i.e., this reducing agents but form salts with metallic and other may be a liquid epoxide, or a solid epoxide in solution) cations, form strongly charged substituted ions in aqueous is added slowly (usually dropwise) while maintaining the 3,395,171 3 4 temperature of the reaction mixture in the range of about of Yi, Y, Y and Y can in combination represent an 10° C. to about 30° C. The reaction is practically instan alicyclic or heterocyclic group. taneous and is controlled by the rate of addition of the Epoxides preferred for use in this invention are those epoxide and by regulating the solution temperature. With having the structural formula very highly reactive epoxides, temperature of 0° C. and 5 even lower may be necessary for reaction rate control O whereas temperatures about 30° C. may be used to in M. N. crease the reaction rate of relatively sluggish epoxides. Y-CH-CE-Y Untried epoxides should be handled by starting the reac tion at a low temperature and gradually warming the re in which Y and Y have the meaning set forth above and action mixture until the desired reaction rate is achieved. O in which Y and Y are functional groups such as those The reaction product is readily recovered by precipitation listed above or radicals containing such functional groups. as an insoluble salt but any convenient recovery proce Such epoxides in which the functional groups are polymer dure such as extraction, distillation and the like can be forming are particularly preferred. The polymer forming used. Cesium in the form of CsP and CsCH is preferred groups can be capable of forming addition polymers or as the precipitating agent, condensation polymers. Following reaction of epoxides Both liquid and solid epoxides can be utilized in this containing polymer forming groups with the acid hydrate invention. Solid epoxides are conveniently dissolved in of hexadecahedral decaborane the polymer can be pro a solvent miscible with the acid hydrate solution to be duced by a conventional reaction. ased in order to facilitate contact between the reactants. 20 Polymers containing the hexadecahedral decaborane Usually both reactants can be dissolved in glyme which unit can also be prepared by the process of the present is accordingly a preferred solvent for practicing this in invention by employing a polymer containing an epoxy vention. Other useful solvents include esters such as group, that is, an epoxide of the above structural Formula methyl acrylate and butyl propionate; dioxane and nitriles 1 in which one or more of Y1, Y2, Y or Ya is a polymer such as acetonitrile and benzonitrile. Preferably the sol radical, that is, a radical formed by removing hydrogen vent used is one in which the acid hydrate dissolves read from a polymer. The polymer can be an addition or a con ily and is miscible with water. Most desirably the solvent densation polymer and is preferably a linear polymer. should also permit recovery of the product by a convenient Polyamides, polyesters and polyureas are preferred con method. densation polymers, being very useful for the formation Epoxides having two or more oxirane groups can also 30 of fibers and films, coatings, finishes and insulation in ap be used in the process of this invention. In these epoxides plications where the presence of the decaborane anion is the oxirane groups can be vicinal or can be separated by desirable.
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