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. one or more intervening atoms. Useful epoxides can be The polymers of this invention contain a Bio group hav mono- or polyfunctional, cyclic or acyclic. Polymeric ing a hexadecahedral structure, usually as a component products are obtainable by using appropriate epoxides, of each recurring unit. This group can be in the polymer that is, epoxides with polymer forming functional groups backbone or in a pendant group. Thus, typical addition or epoxides which are already polymers containing one or polymers have the recurring unit more epoxy groups. Epoxides containing ethylenic un saturation sometimes react with the acid hydrate of hexa decahedral decarborane to produce compounds in which 40 -OR, the epoxide compound moiety, is saturated. Other ---C-C--- orOr ----C-CH wise the oragnic portion of the reaction product usually M y w corersponds to the epoxide reagent used, the epoxy group simply opening up and attaching to a boron of the hexa o Ma b decahedral decaborane by an ether-like linkage. B1Hs In the epoxides useful in this invention Y1, Y2, Y and Y can be the same or different from each other and can be hydrogen or a radical such as an aromatic, aliphatic W or alicyclic group or a heterocyclic group or can be a -CH-CH functional group such as one of the functional groups b. listed below or one of the above-mentioned groups sub where W is a divalent organic radical containing an alkyl stituted with one or more of the following functional enegroup attached to the oxygen in the formula, M, a and groups: b are as defined below, and Z and/or Z is hydrogen or a monovalent radical such as -CN, -COOH, -OH, -C-A -C-CH -C-NA halogen or hydrocarbon such as C, to C14 alkyl, C, to C, O O alkenyl, or Ce to C14 aryl. Typical polymers can also con tain the hexadecahedral Bio group as a pendant group at -C-OA. -C-cCE- -S-A tached to the polymer stem by an ether-like linkage or as O O part of the polymer chain as in polymers with the recurring -C-NA -CC- -i-A 60 unit O (O-W-O-BiH) -CN -C-H. m-SSA, LM, - where M, a and b are as defined below and W is a divalent -X(CI, F, Br) -NO -NHé–OA organic radical having an ethylene group (substituted or not) attached to the oxygens. For linear polymers the group -O-W-O- is a divalent organic radical ob -NA2 -P-(OA) -NCS tained by reacting an epoxide disclosed above containing -SA -OH -NC two epoxide groups (as when one of Y1, Y, Y or Y, con In the above groups A is a monovalent organic radical tains an epoxide group) with an acid hydrate of hexa preferably hydrocarbon, of up to about 15 carbons, which decahedral decaborane according to this invention to open can be alkyl, alkenyl, cycloalkyl, cycloalkenyl, aryl, al both of the epoxide groups. When the epoxide used con karyl, aralkyl and the like. Any of Y1, Y, Y and Y may tains more than two epoxide groups cross linking will contain one or more epoxy groups and any two or more 75 usually result if more than two of the epoxide groups are 3,395,171 5 6 reactive under the conditions used. Stated somewhat dif O ferently, Wis a divalent organic radical having the formula o^ --> -- OCH215 t 3 N

t t / o, where t1, t2, t and t are the same or different and can be CH-CH-CH-O-C-CH=CH hydrogen or a monovalent organic radical sufficiently un O reactive toward epoxide groups to be capable of existence O / N in the compound CH-CH-(CH)-CH O t-cf. SoH-CH, -COC10H2 5 O where t represents each of t, t2, to and t and W' is any divalent organic radical. Polymers of this type can be pre goch, pared by reacting HB10H1'nH2O with a diepoxide in ac Di- (3,4-epoxy-6-methylcyclohexyl-methyladipate) cordance with the present invention. O O All of the polymers referred to may have molecular 20 / / N weights comparable to those of conventional and well known polymers. Persons skilled in polymer chemistry are well aware of the reaction conditions which govern poly mer formation and size and will have no difficulty in pro CH3 H.og (CH), OCH ducing in accordance with this invention polymers suitable 25 for particular applications and requiring specific properties 3,4-epoxy-6-methylcyclohexyl-methyl-3,4-epoxy-6-methylcyclohexane carboxylate in addition to those unique properties contributed by O boron, I Other epoxides useful in this invention include the fol / -CHOC lowing: 30 O O Glycidol - CECH HC-CH-CHOH / 3,4-epoxycyclohexane carbonitrile O N 35 of,M. O You().N. -a- O 40 ( localN / Dipentene dioxide (limonene dioxide) O CH3 O

45

Yo chi / HC N O Yo? 1,2-epoxy-3-phenoxy propane

N / . { X-Ochic O ch, --0-cL. So cir-o-NH-CHNHJ. Dipentene monoxide CHs O N/

60 o( N/Co -'S C (CH)-c-b-o-CH-C H-CH 65 O Alpha-pinene oxide / N CH O (CH5)2N-CH-CH-CH N O -N- 6 N-OH,-off Sch, 70 Y-1 Oct. 1,2-epoxy-3-allyloxy propane --CE-CH-i-L lx O HC CHCHO CHCH=CH / N CH-OCH-CH-CH 75 3,395,171 7 8 12-epoxy-3-(2-allylphenoxy) propane 3,4-epoxy-4-methyl-2-pentanone O O N / / N Hic. O CHCH-0-X >-CHCH=CH, CH3-C-CHCCH3 12-epoxy-3-butoxy propane 5 CI HC CHCHO CH 3-phenyl-2,3-epoxy butyronitrile O O 12-epoxy-3-(2-chloroethoxy) propane CH,04 Sc-C=N CHCHCHOCH2CH2C k i N/ O O 12-epoxy-3-(2-chlorophenoxy) propane Cl CH-CH-CH: ( >-ocHeugh,N/ Yo^ O CH-CH-CH-CII 12-epoxy-3-(4-chlorophenoxy) propane N / N / O O In the above structural formulas x is a whole number, N / 20 C-( >-ochic O toil, usually a large whole number, signifying the number of recurring structural groups in the formula of a polymer 1,2-epoxy-3-(2,4-dichlorophenoxy) propane and b represents a phenyl group. Cl Salts of the derivatives of hexadecahedral decaborane produced by the process of this invention can be obtained by adding compounds capable of forming cations in the reaction product mixture or in a solvent miscible with 12-epoxy-3-ethoxypropane and added to the reaction product mixture. These salts HC CHCHO C2H5 have the structural formula O 30 Ma (B10H10-y(OR) y) b. 1,2-epoxy-3-cyclohexoxypropane where M is a cation; the Bio radical has a hexadecahedral - l structure; -OR is a monovalent organic substituent con nected to a boron atom by an ether-like linkage and cor HicsN/ chiCHox - X- O responding to the epoxide used in the reaction in its 12-epoxy-3-(3-methyl butoxy) propane 3 5 Saturated form with the epoxy ring opened; y is a whole CHCHCHO CHCHCH(CH3) number preferably from 1 to 4 and a and b are positive N/ whole numbers of 1-3 inclusive, whose values are deter O mined by the valence of M such that 12-epoxy-3-(3-methylphenoxy) propane HC 40 b=(valence of M) The -OR groups, when more than one is present, can {Dooney.N/ be the same or different. Where R is a polymeric radical O the above formula would represent a recurring unit in 1,2-epoxy-3-(2-methyl phenoxy) propane the polymer. GH, The corresponding compounds having the formula S-OCH, CH9H, Ma B12H12-y(OR) y o { Y can be prepared by the same reactions under the same 1,2-epoxy-3-methoxy propane 50 conditions utilizing an acid hydrate of an eicosahedral CHCHCHO CH3 N/ decaborane. An acid hydrate of an eicosahedral dodeca O borane (H2B12H12 inH2O) can be prepared by the pro cedure of U.S. Patent 3,169,044, the disclosure of which 12-epoxy-3-pentoxy propane is hereby incorporated into this specification. CH2CHCHO C5H1 5 3 The boron-containing group BioHoy (OR)-2 in the Y above formula is an anion in aqueous solution and be 1,2-epoxy-3-propoxy propane haves as a stable chemical entity in conventional reac CHCHCHOCH7 tions. By varying the amount of epoxide used in the N/ O process of preparation, y may be varied from 1 to 4 or 60 more to produce (BHOR), B1H (OR), Phenyl methyl glycidic ester BioH(OR), B1H6(OR), and higher substituted CH3 hexadecahedral decaborane anions of this type. Since { X-C N /clic OCH3 these anions exhibit detergent properties in aqueous solu O tion the compounds containing more than two (OR) 3,4-epoxy-2,5-dihydrothiophene-1,1-dioxide groups are difficult to recover. Anions of the general formula are conveniently recovered as their insoluble salts such as the cesium salt Cs2B10H10-y(OR); the preferred compound being the salt Cs2B1H3(OR)2. M can be any cation which forms a salt with the 70 BioHoy (OR) in the reaction product mixture. O Where recovery of the boron derivative is not desired, as 1,2-diphenyl ethylene oxide when it is going to be used in solution, the M can be O any cation which produces a salt of the desired solubility ZY. with the anion produced. Exemplary cations include the cis-CICII-b following: hydronium (H3O+), ammonium (NH4), 8,395,171 10 hydrazonium (NH-NH3+), N-substituted ammonium, N-substituted hydrazonium, aryldiazonium, pyridinium, EXAMPLE 1. quinolinium, sulfonium, phosphonium, metal amine, A. Preparation of a decaboryl bis(dialkyl sulfide) lithium, sodium, cesium, beryllium, barium, lanthanum, A reaction vessel having a capacity of about 365 g. of zirconium, vanadium, manganese, iron, cobalt, copper, 5 water is charged with 0.79g. of cup shaped decaborane, Zinc, mercury, aluminum, thallium, tin, lead, antimony; cooled in liquid nitrogen, and then evacuated to a pres bismuth, silver or any other metal, ANHF, ANH2, sure of 10 microns of mercury. Approximately 21 g. of ANHF, AN+, (ANHNH), (AN-NH)+, ASF or methyl sulfide is condensed onto the decaborane in the AP, where A is an organic radical bonded to the nitro reaction vessel. The reaction vessel is closed, allowed to gen, sulfur or phosphorus. The A groups are not critical 0 warm to room temperature and stand for 4 days. Dur features of these cation groups. Substituents represented ing this time, 6.6 millimoles of hydrogen is evolved. The by A can be open-chain or closed-chain, saturated or un reaction vessel is opened and excess methyl sulfide is re saturated, or the groups can be composed of heterocyclic moved by distillation, leaving a practically quantitative rings of which the nitrogen, sulfur or phosphorus is a yield of white solid residue of BioH122(CH3)2S. The component, e.g., pyridine, quinoline, morpholine, hexa 5 compound is recrystallized from ethyl acetate and it melts methyleneimine and the like. Preferably A, for reasons of at 122-124° C. The compound is called bis(dimethyl availability of reactants, represents a hydrocarbon group sulfide) decaborane(10). of up to about 18 carbons. The above procedure is equally operable with other The group M can be a Werner-type coordination com organic sulfides. plex, e.g., a metal amine such as Ni(NH3)6]+, 20 (Zn(NH)3)]+, [Co(NHH-NH2)3]+, [Co(NH3)6]+3 B. Preparation of MB1H (where M is NH4) and the like. Bis(dimethyl sulfide) decaborane(10) (8.5 g.) is mixed The products of this invention may be used in situ or with 50 ml. of liquid ammonia and stirred in a round may be recovered and purified by any convenient means. bottom reaction vessel for one hour with the vessel being Crystallization from aqueous ethanol solutions is usually 25 cooled to a temperature of about -50° C. by partial im effective. For products of limited stability, solutions of mersion in a bath of a mixture of solid carbon dioxide the products can be treated with adsorptive agents, e.g., and acetone. The cooling bath is then removed and the activated charcoal or silica gel to adsorb the major por excess ammonia is allowed to evaporate with stirring. The tion of the impurities. remaining traces of ammonia are removed by subjecting To obtain compounds of this invention having two or 30 the residue to a high vacuum (0.01 mm. of mercury) at more -OR groups which are unlike, the acid hydrate is 25 C. There is obtained 5.6 g. of solid residue which is reacted with one epoxide until the desired number of sub virtually a quantitative yield of diammonium hexadeca stituents are introduced and the partially substituted hedral decaborane (NH4)2B1H10. product is then reacted with a second epoxide. The inter mediate partially substituted product can, if desired, be C. Preparation of H2B10H10 nhO isolated prior to reaction with the second epoxide. The A solution of (NH4)2B1H obtained in part B in 30 process can be repeated with a third epoxide or even ml. of water is passed through a 0.5 inch diameter chroma further. Further modification of various substituent groups tography column containing 80 ml. of a commercial acidic can be accomplished by conventional methods to obtain ion exchange resin ("Amberlite IR 120-H”). The water compounds having a broad range of OR groups. 40 effluent is clear, colorless and acidic. The column is rinsed Salts produced by the process of this invention are with more water until the effluent is no longer acidic and usually solids, many of which dissolve in water. They vary the water fractions are combined. Evaporation of the in stability depending on the substituents and certain nitro combined aqueous solutions under reduced pressure (1 and nitroso containing compounds are sensitive to shock mm. of mercury) at a temperature of about 40° C. leaves and should be kept moist while handling. Others, includ a yellow viscous liquid which is the acid hydrate of hexa ing the halogen-substituted products and hydrocarbon decahedral decaborane (H2BioHo'nH2O). Substituted products, are stable and can be stored for long EXAMPLE 2. periods without extraordinary care. The process of this invention provides a unique method A solution of 2.0 g (0.013 mole) of diammonium hexadecahedral decaborane in 10 ml. of water is passed for introducing a hexadecahedral decaborane with its at 50 through an Amberlite IR 120-H ion exchange column to tendant properties into polymers. As pointed out above, produce the acid hydrate (HaBioHo'nH2O). Water is this is accomplished by utilizing epoxides having polymers evaporated in vacuum at 25° C. and the oily residue dis forming functional groups or other groups convertible Solved in 20 ml. of glyme. A solution of 2.4 g (0.026 into such polymer forming groups. The process is also mole) of epichlorohydrin in 10 ml. of glyme is added useful for introducing hexadecahedral decaborane into a cropwise. The instantaneous reaction is cooled in an ice wide variety of other compounds for applications where bath. The solvent is evaporated in vacuum and the residue a high boron content is desirable. Many of the compounds dissolved in ethanol. Addition of 3.9 g (0.026 mole) of have detergent properties and some are colored permit CSF dissolved in 10 ml. of glyme results in the forma ting their use as pigments or dyes. The decaborane of the tion of a light yellow precipitate. products of this invention possess an aromatic character 60 Analysis shows that one molecule of solvent has also and undergoes reactions in a manner resembling benzene, reacted to give Cs2B10Hs (OCH2CHCHCI) that is, it will react with reagents to add substituents which are capable of bonding to a carbon of an aromatic nucleus (OCH2CHOCH) such as benzene, naphthalene, toluene, etc. Thus, com in which the B10 has a hexadecahedral structure. pounds or anions produced by this invention and in which Calc'd: C, 13.8; H, 4.06; B, 20.9; C1, 6.8. Found: C, the decaborane's hydrogen atoms are not completely re 13.13; H, 4.03; B, 22.01; Cl, 4.03. placed by OR groups, can be reacted with the numerous EXAMPLE 3 reagents suitable for reaction with an aromatic com To a solution of the acid hydrate of hexadecahedral pound to produce a large variety of compounds. 70 decaborane in glyme prepared in Example 1 about 3.1 g. The process of this invention and products produced (0.026 mole) of styrene oxide is added while cooling in thereby are illustrated in the following examples. Prepara an ice bath. The reaction is practically instantaneous at tion of an acid hydrate of hexadecahedral decaborane 37 C. The solvent is evaporated in vacuum to give a dark from commercially available cup shaped decaborane brown gum. This residue is dissolved in 20 ml. of ethanol (BoH14) is shown in Example 1. 75 and 3.9 g. (0.026 mole) of CsF dissolved in ethanol is 3,395,171 11 2 added. A light grey precipitate results. The precipitate is mole) of cesium fluoride in 60 ml. of ethanol is added to recrystallized from an ethanol-water mixture. Elemental precipitate and infrared analyses show the compound to be Cs2B1H8 U C.B.H.(oCHCH-C X) 5 \s in which the B1 has a hexadecahedral structure. in which the B1 has a hexadecahedral structure. The Calc'd: C, 30.78; H, 4.17; B, 17.32. Found: C, 29.32; product is recrystallized from an ethanol-water mixture. H, 4.36; B, 1814. EXAMPLE 4 O EXAMPLE 7 O O A solution of 2.1 g (0.013 mole) of dicyclopentadiene / N CSF dioxide dissolved in 10 ml. of glyme is added dropwise 2Hic-i-clic CH3+ HBioHo'nH2O - to a 20 ml. solution of the acid hydrate of hexadecahedral CH3 decaborane in ethyleneglycoldimethylether prepared as in Example 1. The solution becomes hot (glyme reflux) and H. g . an orange color develops. The solution is then allowed CSB1H8CO (-CHCCH)- to cool to room temperature and the solvent is evaporated CE at reduced pressure. The residual tar is dissolved in eth A solution of 15.4 g. (0.10 mole) of (NH4)2B1H as anol and a solution of 3.9 g (0.026 mole) of CsF added. produced in Example 1B in 40 ml. of water is passed An orange precipitate forms and is isolated. Elemental through an Amberlite IR 120-H. ion exchange column to infrared analyses show the product is produce the acid hydrate H2B1H nEHO. Water is evap orated from the HB1Ho'nH2O solution in vacuum at 20 C. to give a residue of about 20 ml. volume. The acid 2 5 residue is dissolved in 60 mi. of glyme and 22.8 g. (0.20 mole) of 3,4-epoxy-4-methyl-2-pentanone added drop r)" ), JTo wise. The glyme is evaporated in vacuum and the residue in which the B10 has a hexadecahedral structure. dissolved in 60 ml. of ethanol. A solution of 30.4 g (0.20 Calc'd: C, 21.80; H, 4.36; B, 19.60. Found: C, 22.54; 30 mole) of cesium fluoride in 60 ml. of ethanol is added to H, 5.44; B, 19.80. precipitate EXAMPLE 5 CHs o CSBioEs(O (-CH, CH3)2 This example illustrates the following reaction: &H, O O 3 5 / N in which the B10 has a hexadecahedral structure. The (CEIs)3CCOCHCH-CII2 - HBioHon.I.O --> product is recrystallized from an ethanol-water mixture. (1) (2) O -2 EXAMPLE 8 parlo CH2CH2CH2O CC(CH3)3(E+). 40 This example illustrates the reaction of a polymeric (3) epoxide with decahydrodecaborate acid hydrate. hydrolysis CSE CSF (CH-CH) O -- HB110 inHO --> / N CSB10Hs (OCHCHCHOH)2 CHOCH2CH-CH (4) 45 (1) (2) The procedure of Example 3 is followed and the ultimate product anion (4) is recovered by precipitation (Csa)--(CIICH). and identified by elemental and infrared analyses as the L &H.0 CHCH-CHO Bill cesium salt CSBH(OCH2CH2CH2OH) in which the (3) Bo has a hexadecahedral structure. 50 The procedure of Example 3 is followed to produce the Calc'd: C, 7.87; H, 3.5; B, 23.5. Found: C, 7.70; H, product (3) shown. By increasing the quantity of (1) 3.27; B, 18.48. there is produced: EXAMPLE 6 The following reaction is carried out: 55 F.CH-H) - CHOCH2CHCHO BioH-O CHCHC ooch, /On BH /O- CSF (CH-CH)-- 2 -- HBioHo HaO - Cs (CS) S which was characterized by elemental and infrared analy s/ O. W2 60 ses to have the structure shown. O Calcd: C, 23.5; H, 4.9; B, 17.6. Found: C, 23.13; H, A solution of 15.4 g (0.10 mole) of (NH4)2B1Ho 5.3; B, 16.2. (as produced in Example 1B) in 40 ml. of water is passed EXAMPLE 9 through an Amberlite IR 120-H ion exchange column to O 65 / N CSF produce the acid hydrate of hexadecahedral decaborane 2CH3CH-CH - IB1HonEO - Cs2(B10Hs (OC3H)) H2B10H10 mH2O. Water is evaporated from the The reaction is conducted according to the procedure HBioHo nH2O of Example 3 in glyme at a temperature of 30° C. and the product recovered as its cesium salt, Direction of Solution in vacuum at 20 C. to give a residue of about 70 opening of the epoxide ring was shown to occur at both 20 ml. volume. The acid residue is dissolved in 60 ml. of the 1 and 2 position by hydrolysis of glyme and 26.8 g. (0.20 mole) of 3,4-epoxy-2,5-dihydro thiophene-1,1-dioxide added dropwise. Csa BioHa(OCH)2 The gly me is evaporated in vacuum and the residue and identification of both n-propyl and isopropyl alcohol dissolved in 60 ml. of ethanol. A solution of 30.4 g (0.20 75 as derivatives. 3,395,171 13 EXAMPLE 10 EXAMPLE 14 O CSF H3C lo (H, / COCH -- HBioHo'nH2O -) O CSF CS BioH -O N 5 N/ 2 - HBioHo'nHO --> O BioHS- O- --CO. C2H5 Cs2 /'s /'s 10 HC cH, EC cH, 2 N/ 2 A solution of 15.4 g (0.10 mole) of (NH4)2B1H10 as produced in Example 1B in 40 ml. of water is passed The procedure of Example 3 is followed at a tempera through an Amberlite IR 120-H. ion-exchange column to ture of 30° C. in glyme. The product is precipitated and produce the acid hydrate HBioHo'nH2O. Water is evap recovered as its cesium salt. 5 orated from the H2B10H10 inH2O (solution) in vacuum at EXAMPLE 11 a temperature of less than 20° C. to give a residue of CSF about 20 ml. volume. The acid residue is dissolved in 60 CHCH)ct CH, -- H2B10F10-EIO --> ml. of glyme and 30.4 g. (0.20 mole) of dipentene monox ide added dropwise at less than 0° C. Glyme is evaporated 20 in vacuum and the residue dissolve in 60 ml. of ethanol. The reaction was carried out in methyl cyanide accord A solution of 30.4 g (0.20 mole) of cesium fluoride in 60 ing to the procedure of Example 3 at a temperature of ml. of ethanol is added to precipitate 55° C. and the product anion precipitated and recovered CH3 as its cesium salt. Calc'd: C, 30.78; H, 4.17; B, 17.32. Found: C, 29.32; Cs2 B10H8 - O H, 4.36; B, 18.14. EXAMPLE 12 C / N GN GN H3C CH2 30 CSF B10H --O- in which the B1 has a hexadecahedral structure. The 2 -- H2B10H10H2O -> Cs; product is not recrystallized. 2 EXAMPLE 1.5 Nd CSF A solution of 15.4 g. (0.10 mole) of (NH4)2B10H10 (as 2CKXochsche 9H, -- HB 1510-m2O --> produced in Example 1B) in 40 ml. of water is passed O through an Amberlite IR 120-H. ion-exchange column to produce the acid hydrate H2B10H10 mH2O. Water is evap Cs.(BioH (OCH, CH, Og XCI), orated from the HBioHo'nH2O solution in vacuum at a 40 temperature of less than 20 C. to give a residue of about A solution of 15.4 g (0.10 mole) of (NH4)2BioHo as 20 ml. volume. The acid residue is dissolved in 60 ml. of produced in Example 1B in 40 ml. of water is passed glyme and 24.6 g. (0.20 mole) of 3,4-epoxycyclohexane through an Amberlite IR 120-H ion-exchange column to carbonitrile added dropwise at less than 30° C. Glyme produce the acid hydrate H2B10H10 mH2O. Water is evap is evaporated in vacuum and the residue dissolved in 60 orated from the HB1H1'nH2O (solution) in vacuum at ml. of ethanol. A solution of 30.4 g (0.20 mole) of 45 20 C. to give a residue of about 20 ml. volume. The acid cesium fluoride in 60 mi. of ethanol is added to precipi residue is dissolved in 60 ml. of glyme and 33.6 g. (0.20 tate mole) of 1,2-epoxy-3-(4-chlorophenoxy) propane added dropwise. The glyme is evaporated in vacuum and the Cs. BioH or residue dissolved in 60 ml. of ethanol. A solution of 30.4 50 g. (0.2 mole) of cesium fluoride in 60 ml. of ethanol is added to precipitate CNM2 Cs: BioHs(O CHCHCH,0<>C). in which the B1 has a hexadecahedral structure. The 55 product is recrystallized from an ethanol-water mixture. in which the B10 has a hexadecahedral structure. EXAMPLE 13 EXAMPLE 16 -R CSF CSF 2dbOCH2CHCH -- HBioHonEI2O - CS: BioHa (OCH2CH2CH2Op) 60 2CH2CH2CH2O CH3 -- HaBioHo-HO -) A solution of 15.4 g. (0.10 mole) of (NH4)2B10H10 as produced in Example 1B in 40 ml. of water is passed through an Amberlite IR 120-H. ion-exchange column to A solution of 15.4 g. (0.10 mole) of (NH4)2BioHo as produce the acid hydrate H2BioHo'nH2O. Water is evap produced in Example 1B in 40 ml. of water is passed orated from the H2B1Ho'nH2O (solution) in vacuum at 65 through an Amberlite IR 120-H ion-exchange column to a temperature of less than 20° C. to give a residue of produce the acid hydrate H2BioHo'nH2O. Water is evap about 20 ml. volume. The acid residue is dissolved in 60 orated from the HBioHo'nH2O solution in vacuum at ml. of glyme and 30.0 g. (0.20 mole) of 1,2-epoxy-3- 20 C. to give a residue of about 20 ml. volume. The phenoxypropane added dropwise at less than 30 C. acid residue is dissolved in 60 ml. of glyme and 17.6 g. Glyme is evaporated in vacuum and the residue dissolved 70 (0.20 mole) of 1,2-epoxy-3-methoxypropane added drop in 60 ml. of ethanol. A solution of 30 g. (0.20 mole) of wise. The glyme is evaporated in vacuum and the residue cesium fluoride in 60 ml. of ethanol is added to precip dissolved in 60 ml. of ethanol. A solution of 30.4 g (0.20 itate Cs2(B1H8(OCH2CH2CH2Oqb)2 in which the B10 mole) of cesium fluoride in 60 ml. of ethanol is added to has a hexadecahedral structure. The product is recrystal precipitate Cs2B10H8(OCH2CH2CH2OCH) in which lized from ethanol-water mixture. 75 the B10 has a hexadecahedral structure. 3,395,171 15 16 4. The process of claim 2 in which Y is a monovalent EXAMPLE 1.7 polymeric radical having the structural formula, CH CSF 2{ X-lis choolch, -- H2B1Ho-HO. --> ?hti-Yf : O goCH, tort,CHO CE Cs; to CH-CH-) wherein: Z and Z' are individually selected from the group consisting of hydrogen, cyano, carboxylic, hydroxyl, O halogen, Ci to C14 alkyl, C2 to C14 alkenyl and Cs to C4 A solution of 15.4 g (0.10 mole) of (NH4)2B1H as aryl; and x is a large whole number. produced in Example 1B in 40 ml, of water is passed 5. The process of claim 4 in which Y is a monovalent through an Amberlite IR 120-H. ion-exchange column to radical of a condensation polymer. produce the acid hydrate H2BoHo'nH2O. Water is evap 6. The process of claim 4 in which Y is a monovalent orated from the H2B1Ho'nH2O in vacuum at 20° C. to 5 radical of an addition polymer. give a residue of about 20 ml. volume. The acid residue is 7. The process of claim 1 in which the epoxide is sty dissolved in 60 ml. of glyme and 38.4 g (0.20 mole) of rene oxide. phenylmethylglycidic ester added dropwise. The glyme is 8. The process of claim 1 wherein the epoxide is ethyl evaporated in vacuum and the residue dissolved in 60 nml. ene oxide. of ethanol. A solution of 30.4 g. (0.20 mole) of cesium 20 9. The process of claim 1 wherein the epoxide is pro fluoride in 60 ml. of ethanol is added to precipitate pylene oxide. 10. The process of claim 1 wherein the epoxide is di COCEI cyclopentadiene dioxide. CSB18CO (H-H). 11. A linear synthetic organic addition polymer char CE acterized by the recurring structural unit, in which the Bo has a hexadecahedral structure. The prod uct is recrystallized from an ethanol-water mixture. ?, hill What is claimed is: Ma (bH). 1. A process for preparing derivatives of hexadeca 30 hedral decaborane which comprises contacting an acid Bob x hydrate of hexadecahedral decaborane having the for wherein: Z and Z are individually selected from the mula H2BioHo'nHO with an epoxide having the struc group consisting of hydrogen, cyano, carboxylic, hydroxyl, tural formula, 35 halogen, C1 to C14 alkyl, C. to C14 alkenyl and Cs to Ca aryl; the B10 radical has a hexadecahedral structure; M Y-C-C-Y/o, is a cation which forms a salt with the radical Y Y BioHo-y(OR)2 in which Y1, Y, Y and Y are individually selected from 40 a and b are whole numbers of 1-3 inclusive whose values the group of hydrogen and a monovalent radical such are determined by the valence of M and x is a whole that the epoxide is one which is capable of reacting with number. benzene in the presence of an aluminum chloride catalyst 12. A linear synthetic organic condensation polymer at a temperature of less than 100° C. characterized by the recurring structural unit 2. The process of claim 1 in which the reaction is car 45 ried out in an aqueous solution of the acid hydrate of LM, (O-W-O-BiH) - hexadecahedral decaborane. 3. The process of claim 2 in which at least one of where M is a cation which forms a salt with the radical Y and Y is an organic radical with a functional group 50 IB10H10-y(OR), and a and b are whole numbers whose selected from the group of values are determined by the valence of M, the B10 radical has a hexadecahedral structure, W1 is a divalent organic radical with terminal carbon atoms and contains up to -(-A,9 -C-OA, -C-NA, -C=CH, -C=CH-, -CEC about 18 carbon atoms. S O O 55 References Cited -(-NA, -S-A --A, -CN, Cl, F, Br, -N.A., -SA UNITED STATES PATENTS 3,040,010 5/1962 Shokel et al. ------260-2 3,093,660 6/1963. Aftandilian et al. ------260-2 -C-H, -NO, -NC, -P-(OA), -OH, -SSA-, -NEE-oA, -NCS 60 wherein A is a monovalent organic radical of up to about WILLIAM H. SHORT, Primary Examiner. 15 carbon atoms. T. PERTILLA, Assistant Examiner. UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3,395, 171 July 30, 1968 William C. Drinkard, Jr. It is certified that error appears in the above identified patent and that said Letters Patent are hereby corrected as shown below: Column 15, lines 36 to 39, the formula should appear as shown below : /NO Y l a-C G-Y Y 2 Y3 Signed and sealed this 3rd day of February 1970.

(SEAL) Attest: Edward M. Fletcher, Jr. WILLIAM E. SCHUYLER, JR. Attesting Officer Commissioner of Patents