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United States Patent (19) 11) 4,134,923 Reimer 45) Jan United States Patent (19) 11) 4,134,923 Reimer 45) Jan. 16, 1979 54 PROCESS FOR PRODUCING A METAL HYDROXDE ADDUCT OFA OTHER PUBLICATIONS TRARYLBORANE Fowler et al., JACS 62, 1143-1144 (1940). 75 Inventor: Ronald A. Reimer, Orange, Tex. Primary Examiner-Helen M. S. Sneed 57 ABSTRACT 73) Assignee: E. I. Du Pont de Nemours and Company, Wilmington, Del. Process for producing an alkali and/or alkaline earth metal hydroxide adduct of a triarylborane from the 21 Appl. No.: 830,043 amine adduct thereof which comprises reacting an aqueous mixture of said amine adduct with an alkali (22 Filed: Sep. 2, 1977 and/or alkaline earth metal hydroxide at elevated tem perature, e.g., 60-130' C, removing substantially all of 51 Int. Cl2. oooo P. F. P. 8 P. 8 is 8 P. P. 8 8 O. A 4 - 8 woo C07F 5/02 the amine liberated during the reaction, e.g., by strip 52 U.S.C. .............................................. 260/606.5 B ping with an inert gas and thereby forming the metal 58) Field of Search .................................. 260/606.5 B hydroxide adduct of said borane. The process is prefera bly applied to the ammonia adduct of triphenylborane (56) References Cited which adduct is generated in the treatment of a waste U.S. PATENT DOCUMENTS stream from the hydrocyanation process. Sodium is the 3,090,801 5/1963 Washburn et al............. 260/606.5 B preferred metal because the sodium hydroxide adduct is 3,119,857 1/1964 Yates et al..................... 260/606.5 B an intermediate in the production of triarylboranes 3,187,054 1/1965 Willcockson et al. ........ 260/606.5 B which are useful as catalyst promoters. 4,045,495 8/1977 Nazarenko et al. ........... 260/606.5 B 4,046,815 9/1977 Nazarenko et al. ........... 260/606.5 B 6 Claims, 1 Drawing Figure U.S. Patent Jan. 16, 1979 4,134,923 s 0£ 9. 9% 2 801www.d39| ?| |9 8010WW1x3| 02: 92 4,134,923 1. 2 adduct, e.g., as an aqueous slurry with the metal hy PROCESS FOR PRODUCING AMETAL droxide at elevated temperature, e.g., 60-130 C, re HYDROXIDE ADDUCT OF A TRIARYLBORANE moving substantially all of amine liberated during the reaction, e.g., by stripping the solution with an inert gas BACKGROUND OF THE INVENTION 5 such as nitrogen or steam and thereby forming the hy Field of the Invention droxide adduct of the borane. The present invention relates to the recovery and reuse of catalyst components from process residue and DETALED DESCRIPTION OF THE PRESENT more particularly, to a process for preparation of the INVENTION hydroxide adducts of triarylboranes from the amine O It has now been discovered that the hydroxide and adducts of the boranes. The amine adduct, e.g., the amine adducts of the triarylboranes can exist in equilib ammonia adduct of triphenylborane is obtained from rium as illustrated by the following equation for the the treatment of the process residue from the hydrocya ammonia adduct. nation of olefins, e.g., from the preparation of adiponi trile by hydrocyanation of butadiene using nickel or 15 dBNH + OHBOH + NH palladium complexes as catalysts with triphenylborane as the catalyst promoter. The conversion of the ammine adduct to the hydrox ide adduct is accomplished by removing the volatile DESCRIPTION OF THE PRIOR ART amine from the medium under appropriate conditions U.S. Pat. No. 3,119,857 discloses the preparation of 20 and driving the equilibrium to the right side of the organoboron compounds by reacting an organo-alkali above equation to thereby substantially convert all of metal with a boron trihalide or an ester of boric acid in the amine adduct to the hydroxide adduct. an inert liquid reaction medium to produce the corre The amine adducts to which the process of the pres sponding organo boron halide or organo boric acid ent invention can be applied include adducts with vola ester. 25 tile amines such as pyridines; primary and secondary Another process for the preparation of organo boron amines containing up to 12 carbon atoms and tertiary compounds is disclosed in U.S. Pat. No. 3,187,054 amines containing up to 6 carbonatoms. Volatile amines which method involves reacting a boron trihalide, are amines which can be distilled (including azeotropic boron ester or boron-carbon compound with an or distillation) at less than 120° C., optionally under vac ganosodium compound in an inert hydrocarbonsolvent. 30 uum and preferably are amines which have a boiling The preparation of a variety of aryl polyboronic acids point at atmospheric pressure of less than 120° C. Spe and esters by reacting an aromatic halide with finely cific examples of operable amines include ammonia, dispersed metallic sodium in the presence of aborate mono and di methyl and ethyl amine, dodecylamine, esterpreferably at atmospheric pressure and attempera cyclohexylamine, aniline, N-methylaniline, dihexyla tures below about 50 C, is disclosed in U.S. Pat. No, 35 mine, tributylamine, N-butylamine, 2-methylpyridine, 3,090,801. The preparation of sodium hydroxide salt of triphenylborane by reacting triphenylborane with so 2,4-dimethylpyridene and piperidine. dium hydroxide is disclosed by Wittig and Raff in an Although a wide variety of conditions can be em article entitled Uber Komplexibildung mit Triphenyl-bor, ployed to convert the amine to the hydroxide adduct, it Ann, 573 208 (1951). The preparation of related com is preferred to provide a reaction medium which does pounds, e.g., alkyl phosphines, is disclosed in U.S. Pat. not react with, or cause degradation of the amine or the No. 3,223,736, adduct. Preferably the hydroxide adduct is soluble in Some chemistry has been disclosed for the reactions the medium. Examples of suitable media include but are involving the ammonia adduct of triarylborane, Ammo not necessarily limited to water, alcohols containing 1-4 nia displacement from this adduct by reacting the ad carbon atoms and mixtures of the foregoing of which duct with quaternary ammonium fluoride and hydrox water is the preferred medium. ide salts in the presence of ethanol to produce complex The reaction temperature is not critical but elevated salts is disclosed by D. L. Fowler and C. A. Kraus, J. temperatures, e.g., 60-150° C. and preferably 60-130' Am, Chem, Soc., 62, 1143 (1940). This adduct was re C, accelerate the interchange and increase the volatility acted with dry hydrochloric acid in the presence of 50 of the amine for easier removal from the system. Tem ether by Mikhailov et al. Izvest, Akad. Nauk S.S.S.R., peratures in excess of 130 C, can result in increased Otdel. Kimm. Nauk, 812 (1957) to produce triphenyl degradation of the adducts which are quite stable at borane and ammonium chloride. G. Wittig et al. Ann. lower temperatures and can require more complex Chem, 573, 195 (1951) produced triphenylborane by equipment to handle the increased temperatures and thermally decomposing (CH3)3NH--B(C6H5)4- and 55 pressures, further disclose the preparation of the sodium hydrox The pressure under which the reaction is conducted ide salt of triphenylborane by fusion of the borane with may also vary widely but is selected in view of the sodium hydroxide and the reaction of the salt with temperature and the amine to be removed. Pressures in ammonium chloride or hydroxide to yield b3-B NH3. the range of 3 to 40 psia are preferred. The borane was also reacted with sodium cyanide to As should be apparent to those skilled in the art in yield a compound postulated to have the formula view of the above-disclosed equation, the production of b3(CN)BNa. the hydroxide adduct is favored by increased hydroxide concentration in the medium. However, the excess hy SUMMARY OF THE INVENTION droxide must be neutralized before the borane can be A process for producing an alkali and/or alkaline recovered in free form, e.g., as the triarylborane and for earth metal adduct, e.g., the sodium hydroxide adduct this reason it is preferred to employ only slightly more of triarylborane, e.g., triphenylborane from the amine hydroxide than is required to assure substantially com adduct thereof which comprises reacting the amine plete displacement of the amine. In one embodiment of 4,134,923 3 4. the present invention as disucssed in more detail herein "Hexamethylene Diamine' in The Process Economics below, it is preferred to have the product of the present Program Report No. 31-A, Stanford Research Institute, process closely match the intermediate product from Menlo Park, C.A.; September, 1972. More particularly, the borane synthesis to which the hydroxide adduct is the hydrocyanation process is disclosed in U.S. Pat. recycled. In this latter case, the preferred concentration Nos. 3,496,215 issued on Feb. 17, 1970, 3,496,218 issued of hydroxide is in the range 2.5 to 10% by weight based on Nov. 24, 1970, 3,542,847 issued on Nov. 24, 1970, upon the weight of the reaction medium. and 3,752,839 issued on Aug. 14, 1973. The residue from . One preferred embodiment of the present process the above-disclosed process is obtained by removing the involves integration thereof with a process for the prep substantial portion of desired products, unreacted mate aration of triarylboranes. The later process includes O reacting a finely divided alkalimetal, e.g., sodium metal, rials and intermediates from the reactor effluent, sepa having a particle size in the range 1-100 with an aryl rating solvent and other volatiles from the resultant halide, e.g., chlorobenzene and an orthoborate ester, stream for recycle to the reactor and thereafter obtain e.g., those derived from secondary alkyl alcohols, e.g., ing a concentrated waste stream as discussed in more isopropyl alcohol and sec-butyl alcohol in an inert or 15 detail hereinbelow.
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