Abstract:
A method for preparing an amine borane from an alkali metal borohydride and an amine salt. The alkali metal borohydride is allowed to react with 0.95 to 1.05 equivalents of the amine salt in a solvent which contains water and an amine.

Description:
This application claims the benefit of priority under 35 U.S.C. §119(e) of U.S. Provisional Patent Application No. 61/200,218 filed on Nov. 25, 2008. 
     BACKGROUND 
     This invention relates generally to a method for preparing amine boranes from sodium borohydride and an amine salt. 
     Processes for production of amine boranes from sodium borohydride and amine salts are well known, and the reaction usually is carried out in an organic solvent in which sodium borohydride is soluble. For example, U.S. Pat. No. 6,060,623 describes preparation of amine boranes from sodium borohydride and amine salts in an organic solvent, e.g., 1,2-dimethoxyethane. In this process, the initial reaction mixture must be distilled to remove the solvent prior to isolation of the amine borane product. 
     The problem addressed by this invention is to provide a more efficient process for producing amine boranes from sodium borohydride and amine salts, without the use of additional solvents for the borohydride starting material. 
     STATEMENT OF INVENTION 
     The present invention is directed to a method for preparing amine boranes from an alkali metal borohydride and an amine salt. The method comprises allowing the alkali metal borohydride to react with 0.95 to 1.05 equivalents of the amine salt in a solvent comprising: (i) an amine which is a basic form of the amine salt; and (ii) water; wherein a weight ratio of total water in the solvent to alkali metal borohydride is from 0.5:1 to 2.7:1; and wherein the solvent contains no more than 5 wt % of solvents other than water and the amine. 
    
    
     DETAILED DESCRIPTION 
     Unless otherwise specified, all percentages herein are stated as weight percentages and temperatures are in ° C. Amounts in parts per million (ppm) are on the basis of weight/volume. In cases where the alkali metal borohydride is added as a dihydrate, ratios of amounts relative to an amount of alkali metal borohydride are relative to the contained alkali metal borohydride and not the dihydrate. 
     An “alkyl” group is a saturated hydrocarbyl group having from one to twenty carbon atoms, and may be linear, branched or cyclic. In some embodiments of the invention, alkyl groups are linear or branched, alternatively they are linear. In some embodiments, alkyl groups have from one to six carbon atoms, alternatively from one to four carbon atoms. A “hydrocarbon solvent” is any material essentially containing only carbon and hydrogen and which is a liquid at 0° C. at a pressure of 100 kPa. Hydrocarbon solvents may contain trace levels, i.e., less than 0.5%, of elements other than carbon and hydrogen as impurities. In some embodiments of the invention, hydrocarbon solvents are aliphatic hydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbons or mixtures thereof; alternatively, saturated aliphatic hydrocarbons and/or aromatic hydrocarbons, alternatively C 4 -C 16  saturated aliphatic hydrocarbons and/or C 7 -C 20  aromatic hydrocarbons. Aromatic hydrocarbons are those containing an aromatic ring, which may have alkyl substituents. Especially preferred hydrocarbon solvents include mineral oil, toluene, xylenes, ethylbenzene, C 6 -C 16  saturated aliphatic hydrocarbons, and mixtures thereof. 
     The reaction of an alkali metal borohydride with an amine is shown in general form in the following equation
 
MBH 4 +HA+R 3 N→R 3 NBH 3 +MA+H 2  
 
wherein M is an alkali metal cation; A is a conjugate base derived from a mineral acid, boric acid or carbonic acid and R may represent the same or different alkyl groups and/or hydrogen, provided that at least two alkyl groups are present. Preferably, the alkyl groups are C 1 -C 4  alkyl groups, alternatively methyl or ethyl. Preferably, R does not represent hydrogen, and the amine is a trialkylamine. Preferably, M is sodium or potassium. Preferably the acid, HA is hydrochloric acid or sulfuric acid. In some embodiments, the amine hydrochloride is pre-formed, and the equation becomes
 
MBH 4 +R 3 NHA→R 3 NBH 3 +MA+H 2  
 
In these embodiments, preferably free amine and water are added as solvents.
 
     The solvent, as the term is used herein, includes all water present, including any water of hydration from the alkali metal borohydride, and any water present in aqueous acid, in those embodiments where the amine salt is generated in situ from the amine and an acid. Preferably, the weight ratio of water in the solvent to the alkali metal borohydride is at least 0.7:1, alternatively at least 0.8:1, alternatively at least 0.9:1, alternatively at least 1:1, alternatively at least 1.5:1; preferably the ratio is no more than 2.5:1, alternatively no more than 2.2:1, alternatively no more than 2:1. 
     Preferably, the reaction occurs at a temperature in the range from 5° C. to 5° C. below the atmospheric-pressure boiling point of the solvent. In some embodiments, the temperature is at least 10° C., alternatively at least 15° C.; and preferably no greater than 100° C., alternatively no greater than 70° C., alternatively no greater than 50° C. 
     In some embodiments of the invention, the solvent contains no more than 5% of any solvent other than water and said amine. In these embodiments, preferably the weight ratio of total water in the solvent to alkali metal borohydride is from 0.5:1 to 2.7:1, alternatively from 0.8:1 to 2.7:1, alternatively from 1:1 to 2.7:1, alternatively from 1.5:1 to 2.7:1, alternatively from 1:1 to 2.5:1, alternatively from 1.5:1 to 2.5:1. In these embodiments, preferably the alkali metal borohydride is sodium borohydride which is introduced in the form of its dihydrate. In these embodiments, preferably, the weight ratio of free amine, i.e., amine not in the form of a salt, to alkali metal borohydride is from 1:1 to 6:1, alternatively from 1.5:1 to 6:1, alternatively from 2:1 to 6:1, alternatively from 2:1 to 5:1, alternatively from 2.5:1 to 4.5:1. 
     In some embodiments of the invention, the solvent further comprises a hydrocarbon solvent or a combination of hydrocarbon solvents. In these embodiments, preferably the weight ratio of total water to alkali metal borohydride is from 0.5:1 to 2.5:1, alternatively from 0.5:1 to 2:1, alternatively from 0.7:1 to 2:1, alternatively from 0.7:1 to 1.5:1. In these embodiments, preferably the weight ratio of hydrocarbon solvent(s) to alkali metal borohydride is from 1.5:1 to 12:1, alternatively from 2:1 to 12:1, alternatively from 2:1 to 10:1, alternatively from 1.5:1 to 8:1 In these embodiments, preferably the hydrocarbon solvent(s) is from 25 wt % to 70 wt % of the total weight of reactants and solvents, alternatively from 30 wt % to 65 wt %, alternatively from 30 wt % to 60 wt %, alternatively from 35 wt % to 60 wt %. In these embodiments, preferably the total amine, free amine plus the weight of amine contained in an amine salt, is at least 20 wt % of the total weight of reactants and solvents, alternatively at least 22 wt %, alternatively at least 24 wt %; and preferably no more than 40 wt %, alternatively no more than 36 wt %, alternatively from no more than 34 wt %. In these embodiments, preferably the total water, free water plus the weight of water contained in aqueous acid or hydrates, is at least 5 wt % of the total weight of reactants and solvents, alternatively at least 6 wt %, alternatively at least 7 wt %, alternatively at least 8 wt %; and preferably no more than 15 wt %, alternatively no more than 14 wt %, alternatively from no more than 13 wt %, alternatively no more than 12 wt %. 
     Preferably, the solvent contains no more than 5%, alternatively no more than 2% of solvents in which the alkali metal borohydride is soluble to an extent of at least 2%. Solvents in which alkali metal borohydrides are soluble include C 3 -C 8  aliphatic amines, C 3 -C 8  cyclic amines, C 3 -C 8  diamines, C 3 -C 8  alkanolamines, C 5 -C 10  aromatic amines, C 4 -C 12  methyl ethers of ethylene glycol and ethylene glycol oligomers, and C 2 -C 8  amides. The aliphatic amines include mono-, di- and tri-alkyl amines, especially mono-alkyl amines, especially primary and secondary mono-alkyl amines. The aromatic amines include pyridine. The best amide solvents include N,N-dialkyl amides, especially aliphatic amides. Commonly used solvents include n-propylamine, isopropylamine, isobutylamine, sec-butylamine, n-butylamine, n-pentylamine, 1,2-dimethoxyethane, diethylene glycol dimethyl ether, pyridine, dimethylformamide, and dimethylacetamide. 
     EXAMPLES 
     Solid Sodium Borohydride with Solid Triethylamine Hydrochloride (NEt 3 HCl) in Toluene at Room Temperature 
     A three-neck flask containing a solids addition funnel, thermometer and a nitrogen gas purge was charged with 10 grams of SBH AF Grans (SBH with particle size larger than 80 mesh and smaller than 40 mesh). Then 100 mL of anhydrous toluene and 30 mL of NEt 3  were added. This slurry was stirred and 1 equivalent of solid NEt 3 HCl (36.2 g) was added. No gas was evolved during the addition process. The reaction was stopped. No reaction; Yield=0%. 
     Sodium Borohydride in Isopropylamine and Solid NEt 3 HCl 
     A three-neck flask containing a solids addition funnel, thermometer and a nitrogen gas purge was charged with 10 grams of SBH AF Grans, 90 grams of isopropylamine and 50 mL triethylamine. The resulting solution was stirred and 1 equivalent of solid NEt 3 HCl (36.2 g) was added over a 3 hour period. Gas was instantaneously produced upon adding the solid NEt 3 HCl. After the addition was completed, the slurry was stirred for an additional 3 hours at which time 50 mL of deionized water was added. The resulting two-phase solution was placed into a separatory funnel. Both the isopropylamine and water phases were analyzed by  1 H and  11 B NMR. The top isopropylamine layer contained 98% NH 2   i PrBH 3  and 2% NEt 3 BH 3 . 
     Spectroscopic data for NEt 3 BH3:  11 B NMR (tol d 8 ), δ-30.8 ppm, (q, J B-H =98.3 Hz, 1B).  1 H (tol d 8 ) δ=2.32 ppm (q, j 1-3 =7.2 Hz, 6H) δ 0.84 ppm, (t, J H-H =7.3 Hz, 9H) 
     Spectroscopic data for NH 2   i PrBH 3 :  11 B (tol d 8 )=-38.7 ppm (q, J B- H =94.5 Hz., 1B)  1 H (tol d 8 ) ε=2.66 ppm, (sep, 1H, J H-H =6.45 Hz); δ=2.27 ppm,(dd, J H-H =4.5 Hz, 2H); δ 1.42 ppm, (s, 3H); δ 0.92 ppm, (d, 6H J H-H =9.26 Hz) 
     Synthetic Sodium Borohydride Dihydrate with 100 mL Toluene and Solid NEt 3 HCl 
     A three-neck flask containing a solids addition funnel, thermometer and a nitrogen gas purge was charged with 10 grams of SBH AF Grans, 10 grams of water and 0.1 grams of NaOH. The slurry was stirred for 24 hours until a solid mass formed. Then 100 mL of anhydrous toluene and 30 mL of NEt 3  were added. This slurry was stirred and 1 equivalent of solid NEt 3 HCl (36.2 g) was added so that the temperature of the reaction did not increase above 40° C. 
     A large amount of gas evolved when the temperature of the reaction rose above 30° C. After 6 hours, 60 mL of water were added to dissolve all of the solids in the reaction pot. The resulting two-phase solution was placed into a separatory funnel and the bottom phase was washed with 3×100 mL of fresh toluene. All of the toluene phases were combined. Both the toluene and water phases were analyzed by  1 H and  11 B NMR. 
     Spectroscopic data for NEt 3 BH 3 .  11 B NMR (tol d 8 ), δ-30.8 ppm, (q, J B-H =98.3 Hz, 1B).  1 H (tol d 8 ) δ=2.32 ppm (q, j 1-3 =7.2 Hz, 6H) δ 0.84 ppm, (t, J H-H =7.3 Hz, 9H) 
     
       
         
               
               
               
               
             
               
               
               
               
               
             
               
               
               
             
           
               
                   
               
               
                 Material 
                   
                 Amount 
                 Total amount 
               
               
                 charged 
                 Amount charged 
                 recovered 
                 recovered 
               
               
                   
               
             
             
               
                   
               
             
          
           
               
                 SBH AF Grans 
                 10.0 
                 g 
                   
                   
               
               
                 Water 
                 10.0 
                 g 
               
               
                 NEt 3   
                 25 
                 g 
               
               
                 Toluene 
                 100 
                 mL (86.5 g) 
                 123.76 g 
               
               
                 NEt 3 HCl 
                 36.2 
                 g 
               
               
                 Water added 
                 60 
                 mL (60 g) 
                   
                  87.88 g 
               
               
                 Toluene wash 1 
                 100 
                 mL (86.5 g) 
                  56.5 g 
               
               
                 Toluene wash 2 
                 100 
                 mL (86.5 g) 
                  70.50 g 
               
               
                 Toluene wash 3 
                 100 
                 mL (86.5 g) 
                 100.27 g 
                 383.03 g 
               
             
          
           
               
                 Yield 
                 98% 
               
               
                   
               
             
          
         
       
     
     Synthetic Sodium Borohydride Dihydrate with 50 mL of Toluene and Solid NEt 3 HCl 
     A three-neck flask containing a solids addition funnel, thermometer and a nitrogen gas purge was charged with 10 grams of SBH AF Grans and 10 grams of water with 0.1 grams of NaOH. The slurry was stirred for 24 hours until a solid mass formed. Then 50 mL of anhydrous toluene and 10 mL of NEt 3  were added. This slurry was stirred and 1 equivalent of solid NEt 3 HCl (36.3 g) was added so that the temperature of the reaction did not increase above 40° C. 
     A large amount of gas evolved when the temperature of the reaction rose above 30° C. After 6 hours, 60 mL of water were added to dissolve all of the solids in the reaction pot. The resulting two-phase solution was placed into a separatory funnel and the bottom phase was washed with 3×30 mL of fresh toluene. All of the toluene phases were combined. Both the toluene and water phases were analyzed by  1 H and  11 B NMR. 
     Spectroscopic data for NEt 3 BH 3 .  11 B NMR (tol d 8 ), δ-30.8 ppm, (q, J B-H =98.3 Hz, 1B).  1 H (tol d 8 ) δ=2.32 ppm (q, j 1-3 =7.2 Hz, 6H) δ 0.84 ppm, (t, J H-H =7.3 Hz, 9H) 
     
       
         
               
               
               
               
             
               
               
               
               
               
             
               
               
               
             
           
               
                   
               
               
                 Material 
                   
                 Amount 
                 Total amount 
               
               
                 charged 
                 Amount charged 
                 recovered 
                 recovered 
               
               
                   
               
             
             
               
                   
               
             
          
           
               
                 SBH AF Grans 
                 10.0 
                 g 
                   
                   
               
               
                 Water 
                 10.0 
                 g 
               
               
                 NEt 3   
                 10 
                 mL (7.26 g) 
               
               
                 Toluene 
                 50 
                 mL (43.5 g) 
                 73.25 g 
               
               
                 NEt 3 HCl 
                 36.3 
                 g 
               
               
                 Water added 
                 60 
                 mL (60.0 g) 
                   
                  82.43 g 
               
               
                 Toluene wash 1 
                 30 
                 mL (25.95 g) 
                 26.89 g 
               
               
                 Toluene wash 2 
                 30 
                 mL (25.95 g) 
                 19.90 g 
               
               
                 Toluene wash 3 
                 30 
                 mL (35.95 g) 
                 25.74 g 
                 145.77 g 
               
             
          
           
               
                 Yield 
                 98% 
               
               
                   
               
             
          
         
       
     
     Synthetic Sodium Borohydride Dihydrate with 50 mL Dodecane and Solid NEt 3 HCl (to Little NEt 3 HCl Added) 
     A three-neck flask containing a solids addition funnel, thermometer and a nitrogen gas purge was charged with 10 grams of SBH AF Grans and 10 grams of water with 0.1 grams of NaOH. The slurry was stirred for 24 hours until a solid mass formed. Then 50 mL of anhydrous dodecane and 10 mL of NEt 3  were added. This slurry was stirred and 1 equivalence of solid NEt 3 HCl (26.4 g) was added so that the temperature of the reaction did not increase above 40° C. 
     A large amount of gas evolved when the temperature of the reaction rose above 30° C. After 6 hours, 60 mL of water were added to dissolve all of the solids in the reaction pot. The resulting two-phase solution was placed into a separatory funnel and the bottom phase was washed with 3×30 mL of fresh toluene. All of the toluene phases were combined. Both the dodecane and water phases were analyzed by  1 H and  11 B NMR. 
     Spectroscopic data for NEt 3 BH 3 .  11 B NMR (tol d 8 ), δ-30.8 ppm, (q, J B-H =98.3 Hz, 1B).  1 H (tol d 8 ) δ=2.32 ppm (q, j 1-3 =7.2 Hz, 6H) δ 0.84 ppm, (t, J H-H =7.3 Hz, 9H) 
     
       
         
               
               
               
               
             
               
               
               
               
               
             
               
               
               
             
           
               
                   
               
               
                 Material 
                 Amount 
                 Amount 
                 Total amount 
               
               
                 charged 
                 charged 
                 recovered 
                 recovered 
               
               
                   
               
             
             
               
                   
               
             
          
           
               
                 SBH AF Grans 
                 10.16 
                 g 
                   
                   
               
               
                 Water 
                 10.0 
                 g 
               
               
                 NEt 3   
                 10 
                 mL (7.26 g) 
               
               
                 dodecane 
                 50 
                 mL (37.5 g) 
                 65.15 g 
               
               
                 NEt 3 HCl 
                 26.4 
                 g 
               
               
                 Water added 
                 60 
                 mL 
                   
                  73.21 g 
               
               
                 Dodecane wash 1 
                 30 
                 mL (22.5 g) 
                 21.20 g 
               
               
                 Dodecane wash 2 
                 30 
                 mL (22.5 g) 
                 23.37 g 
               
               
                 Dodecane wash 3 
                 30 
                 mL (22.5 g) 
                 27.80 g 
                 137.50 g 
               
             
          
           
               
                 Yield 
                 44% 
               
               
                   
               
             
          
         
       
     
     KBH 4  and 50 mL Toluene and Solid NEt 3 HCl 
     A three-neck flask containing a solids addition funnel, thermometer and a nitrogen gas purge was charged with 14.21 grams of KBH 4  100 and 10 grams of water with 0.1 grams of NaOH. Then 50 grams of anhydrous toluene and 10 mL of NEt 3  were added. This slurry was stirred and 1 equivalent of solid NEt 3 HCl (36.2 g) was added so that the temperature of the reaction did not increase above 40° C. 
     A large amount of gas evolved when the temperature of the reaction rose above 30° C. After 6 hours, 60 mL of water were added to dissolve all of the solids in the reaction pot. The resulting two-phase solution was placed into a separatory funnel and the bottom phase was washed with 3×30 mL of fresh toluene. All of the toluene phases were combined. Both the toluene and water phases were analyzed by  1 H and  11 B NMR. 
     Spectroscopic data for NEt 3 BH 3 .  11 B NMR (tol d 8 ), δ-30.8 ppm, (q, J B-H =98.3 Hz, 1B).  1 H (tol d 8 ) δ=2.32 ppm (q, j 1-3 =7.2 Hz, 6H) δ 0.84 ppm, (t, J H-H =7.3 Hz, 9H) 
     
       
         
               
               
               
               
             
               
               
               
               
               
             
               
               
               
             
           
               
                   
               
               
                 Material 
                   
                 Amount 
                 Total amount 
               
               
                 charged 
                 Amount charged 
                 recovered 
                 recovered 
               
               
                   
               
             
             
               
                   
               
             
          
           
               
                 KBH 4  100 
                 14.21 
                 g 
                   
                   
               
               
                 Water 
                 10 
                 g 
               
               
                 NEt 3   
                 10 
                 mL (7.26 g) 
               
               
                 Toluene 
                 50 
                 mL (43.5 g) 
                 69.52 g 
               
               
                 NEt 3 HCl 
                 36.2 
                 g 
               
               
                 Water added 
                 60 
                 mL (60 g) 
                   
                  88.85 g 
               
               
                 Toluene wash 1 
                 30 
                 mL (25.95 g) 
                 20.96 g 
               
               
                 Toluene wash 2 
                 30 
                 mL (25.95 g) 
                 21.82 g 
               
               
                 Toluene wash 3 
                 30 
                 mL (25.95 g) 
                 27.34 g 
                 139.64 g 
               
             
          
           
               
                 Yield 
                 93% 
               
               
                   
               
             
          
         
       
     
     Synthetic Sodium Borohydride Dihydrate with 25 mL Toluene and Solid NEt 3 HCl 
     A three-neck flask containing a solids addition funnel, thermometer and a nitrogen gas purge was charged with 10 grams of SBH AF Grans and 10 grams of water with 0.1 grams of NaOH. The slurry was stirred for 24 hours until a solid mass formed. Then 25 mL of anhydrous toluene and 5 mL of NEt 3  were added. This slurry was stirred and 1 equivalent of solid NEt 3 HCl (36.2 g) was added so that the temperature of the reaction did not increase above 40° C. 
     A large amount of gas evolved when the temperature of the reaction rose above 30° C. After 6 hours, 60 mL of water were added to dissolve all of the solids in the reaction pot. The resulting two-phase solution was placed into a separatory funnel and the bottom phase was washed with 3×30 mL of fresh toluene. All of the toluene phases were combined. Both the toluene and water phases were analyzed by  1 H and  11 B NMR. 
     Spectroscopic data for NEt 3 BH 3 .  11 B NMR (tol d 8 ), δ-30.8 ppm, (q, J B-H =98.3 Hz, 1B).  1 H (tol d 8 ) δ=2.32 ppm (q, j 1-3 =7.2 Hz, 6H) δ 0.84 ppm, (t, J H-H =7.3 Hz, 9H) 
     
       
         
               
               
               
               
             
               
               
               
               
               
             
               
               
               
             
           
               
                   
               
               
                 Material 
                 Amount 
                 Amount 
                 Total amount 
               
               
                 charged 
                 charged 
                 recovered 
                 recovered 
               
               
                   
               
             
             
               
                   
               
             
          
           
               
                 SBH AF Grans 
                 10.16 
                 g 
                   
                   
               
               
                 Water 
                 10.0 
                 g 
               
               
                 NEt 3   
                 5 
                 mL (3.63 g) 
               
               
                 Toluene 
                 25 
                 mL (21.62 g) 
                 49.29 g 
               
               
                 NEt 3 HCl 
                 36.2 
                 g 
               
               
                 Water added 
                 60 
                 mL 
                 72.44 g 
                 72.44 g 
               
               
                 Toluene wash 1 
                 15 
                 mL (12.97 g) 
                 16.15 g 
               
               
                 Toluene wash 2 
                 15 
                 mL (12.97 g) 
                 16.16 g 
               
               
                 Toluene wash 3 
                 15 
                 mL (12.97 g) 
                 16.23 g 
                 97.81 g 
               
             
          
           
               
                 Yield 
                 98% 
               
               
                   
               
             
          
         
       
     
     Synthetic Sodium Borohydride Dihydrate with 25 mL Xylenes and Solid NEt 3 HCl 
     A three-neck flask containing a solids addition funnel, thermometer and a nitrogen gas purge was charged with 10 grams of SBH AF Grans and 10 grams of water with 0.1 grams of NaOH. The slurry was stirred for 24 hours until a solid mass formed. Then 25 mL of anhydrous xylenes and 5 mL of NEt 3  were added. This slurry was stirred and 1 equivalent of solid NEt 3 HCl (36.2 g) was added so that the temperature of the reaction did not increase above 40° C. 
     A large amount of gas evolved when the temperature of the reaction rose above 30° C. After 6 hours, 60 mL of water were added to dissolve all of the solids in the reaction pot. The resulting two-phase solution was placed into a separator funnel and the bottom phase was washed with 3×30mL of fresh xylenes. All of the xylenes phases were combined. Both the xylenes and water phases were analyzed by  1 H and  11 B NMR. 
     Spectroscopic data for NEt 3 BH 3 .  11 B NMR (tol d 8 ), δ-30.8 ppm, (q, J B-H =98.3 Hz, 1B).  1 H (tol d 8 ) δ=2.32 ppm (q, j 1-3 =7.2 Hz, 6H) δ 0.84 ppm, (t, J H-H =7.3 Hz, 9H) 
     
       
         
               
               
               
               
             
               
               
               
               
               
             
               
               
               
             
           
               
                   
               
               
                 Material 
                 Amount 
                 Amount 
                 Total amount 
               
               
                 charged 
                 charged 
                 recovered 
                 recovered 
               
               
                   
               
             
             
               
                   
               
             
          
           
               
                 SBH AF Grans 
                 10.10 
                 g 
                   
                   
               
               
                 Water 
                 10.0 
                 g 
               
               
                 NEt 3   
                 5 
                 mL (3.63 g) 
               
               
                 Xylenes 
                 25 
                 mL (21.5 g) 
                 48.56 g 
               
               
                 NEt 3 HCl 
                 36.2 
                 g 
               
               
                 Water added 
                 60 
                 mL 
                 61.19 g 
                 61.19 g 
               
               
                 Xylenes wash 1 
                 15 
                 mL (12.9 g) 
                 17.70 g 
               
               
                 Xylenes wash 2 
                 15 
                 mL (12.9 g) 
                 7.29 g 
               
               
                 Xylenes wash 3 
                 15 
                 mL (12.9 g) 
                 5.17 g 
                 78.75 g 
               
             
          
           
               
                 Yield 
                 98% 
               
               
                   
               
             
          
         
       
     
     Synthetic Sodium Borohydride Dihydrate with 25 mL Triethylamine and Solid NEt 3 HCl 
     A three-neck flask containing a solids addition funnel, thermometer and a nitrogen gas purge was charged with 10 grams of SBH AF Grans and 10 grams of water with 0.1 grams of NaOH. The slurry was stirred for 24 hours until a solid mass formed. Then 25 mL of anhydrous triethylamine was added. This slurry was stirred and 1 equivalent of solid NEt 3 HCl (36.2 g) was added so that the temperature of the reaction did not increase above 40° C. 
     A large amount of gas evolved when the temperature of the reaction rose above 30° C. After 6 hours, 60 mL of water were added to dissolve all of the solids in the reaction pot. The resulting two-phase solution was placed into a separator funnel and the bottom phase was washed with 3×5 mL of fresh NEt 3 . All of the triethyl amine phases were combined. Both the triethylamine and water phases were analyzed by  1 H and  11 B NMR. 
     Spectroscopic data for NEt 3 BH 3 .  11 B NMR (tol d 8 ), δ-30.8 ppm, (q, J J-H =98.3 Hz, 1B).  1 H (tol d 8 ) δ=2.32 ppm (q, j 1-3 =7.2 Hz, 6H) δ 0.84 ppm, (t, J H-H =7.3 Hz, 9H) 
     
       
         
               
               
               
               
             
               
               
               
               
               
             
               
               
               
             
           
               
                   
               
               
                 Material 
                 Amount 
                 Amount 
                 Total amount 
               
               
                 charged 
                 charged 
                 recovered 
                 recovered 
               
               
                   
               
             
             
               
                   
               
             
          
           
               
                 SBH AF 
                 10.10 
                 g 
                   
                   
               
               
                 Grans 
               
               
                 Water 
                 10.0 
                 g 
               
               
                 NEt 3   
                 25 
                 mL (18.15 g) 
                 33.52 g  
               
               
                 NEt 3 HCl 
                 36.2 
                 g 
               
               
                 Water added 
                 60 
                 mL 
                 55.0 g 
                  55.0 g 
               
               
                 NEt 3  wash 1 
                 5 
                 mL (3.63 g) 
                 0.55 g 
               
               
                 NEt 3  wash 2 
                 5 
                 mL (3.63 g) 
                 2.92 g 
               
               
                 NEt 3  wash 3 
                 5 
                 mL (3.63 g) 
                 3.19 g 
                 40.18 g 
               
             
          
           
               
                 Yield 
                 96% 
               
               
                   
               
             
          
         
       
     
     Synthetic Sodium Borohydride Dihydrate with 100 mL Toluene and Preformed NEt 3 HCl 
     A three-neck flask containing a solids addition funnel, thermometer and a nitrogen gas purge was charged with 10 grams of SBH AF Grans, 10 grams of water and 0.1 grams of NaOH. The slurry was stirred for 24 hours until a solid mass formed. Another three-neck flask was charged with 1 eq of NEt 3  and 1 eq of 37% HCl. Then 100 mL of anhydrous toluene and 30 mL of NEt 3  were added. This slurry was stirred and the content of flask number one was added so that the temperature of the reaction did not increase above 40° C. 
     A large amount of gas evolved when the temperature of the reaction rose above 30° C. After 6 hours, 60 mL of water were added to dissolve all of the solids in the reaction pot. The resulting two-phase solution was placed into a separatory funnel and the bottom phase was washed with 3×100 mL of fresh toluene. All of the toluene phases were combined. Both the toluene and water phases were analyzed by  1 H and  11 B NMR. 
     Spectroscopic data for NEt 3 BH 3 .  11 B NMR (tol d 8 ), δ-30.8 ppm, (q, J B-H =98.3 Hz, 1B).  1 H (tol d 8 ) δ=2.32 ppm (q, j 1-3 =7.2 Hz, 6H) δ 0.84 ppm, (t, J H-H =7.3 Hz, 9H) 
     
       
         
               
               
               
               
             
               
               
               
               
               
             
               
               
               
             
           
               
                   
               
               
                 Material 
                   
                 Amount 
                 Total amount 
               
               
                 charged 
                 Amount charged 
                 recovered 
                 recovered 
               
               
                   
               
             
             
               
                   
               
             
          
           
               
                 SBH AF Grans 
                 10.30 
                 g 
                   
                   
               
               
                 Water 
                 10.0 
                 g 
               
               
                 NEt 3   
                 86.5 
                 mL (62.80 g) 
               
               
                 Toluene 
                 50 
                 mL (43.25 g) 
                 105.97 g  
               
               
                 39% HCl 
                 21.74 
                 mL 
               
               
                 Water added 
                 60 
                 mL (60 g) 
                   
                 105.74 g 
               
               
                 Toluene wash 1 
                 100 
                 mL (86.5 g) 
                 86.17 g 
               
               
                 Toluene wash 2 
                 100 
                 mL (86.5 g) 
                 77.86 g 
               
               
                 Toluene wash 3 
                 100 
                 mL (86.5 g) 
                 78.64 g 
                 348.64 g 
               
             
          
           
               
                 Yield 
                 54% 
               
               
                   
               
             
          
         
       
     
     The following table summarizes the experiments above and the results. 
     
       
         
               
             
               
               
               
               
               
               
               
               
               
               
             
               
               
               
               
               
               
               
               
               
               
             
           
               
                 TABLE 1 
               
             
             
               
                   
               
               
                 Synthesis of NEt 3 BH 3  (1) 
               
             
          
           
               
                   
                   
                   
                   
                   
                   
                   
                   
                   
                 % 
               
               
                   
                   
                   
                   
                   
                   
                   
                   
                   
                 Yield 
               
               
                   
                   
                 excess 
                   
                   
                   
                   
                   
                   
                 NEt 3   
               
               
                   
                   
                 NEt 3   
                   
                 form 
                   
                 Form 
                   
                 react. 
                 BH 3   
               
               
                   
                   
                 added, 
                 cont. 
                 of 
                   
                 of 
                 wash, 
                 temp. 
                 By 
               
               
                 Solvent 
                 g 
                 mL 
                 SBH, g 
                 SBH 
                 NEt 3 •HCl 
                 NEt 3 •HCl 
                 mL 
                 ° C. 
                 NMR 
               
               
                   
               
             
          
           
               
                 isopropyl 
                 90 
                 50 
                 10 
                 Pure 
                 1 eq 
                 solid 
                 0 
                 22 
                 2 
               
               
                 amine 
               
               
                 toluene 
                 100 
                 50 
                 10 
                 Pure 
                 1 eq 
                 solid 
                 0 
                 22 
                 0 
               
               
                 toluene 
                 100 
                 25 
                 10 
                 •2H 2 O 
                 1 eq 
                 solid 
                  3 × 100 
                 22-40 
                 98 
               
               
                 toluene 
                 50 
                 10 
                 10 
                 •2H 2 O 
                 1 eq 
                 solid 
                 3 × 30 
                 22-40 
                 98 
               
               
                 dodecane 
                 50 
                 25 
                 10 
                 •2H 2 O 
                 0.72 eq   
                 solid 
                 3 × 30 
                 22-40 
                 54 
               
               
                 toluene 
                 50 
                 25 
                 14.21 
                 KBH 4   
                 1 eq 
                 solid 
                 3 × 30 
                 22-40 
                 93 
               
               
                 toluene 
                 25 
                 5 
                 10 
                 •2H 2 O 
                 1 eq 
                 solid 
                 3 × 15 
                 22-40 
                 98 
               
               
                 xylenes 
                 25 
                 5 
                 10 
                 •2H 2 O 
                 1 eq 
                 solid 
                 3 × 15 
                 22-40 
                 98 
               
               
                 NEt 3   
                 25 
                 0 
                 10 
                 •2H 2 O 
                 1 eq 
                 solid 
                 3 × 5  
                 22-40 
                 96 
               
               
                 NEt 3   
                 50 
                 21.71 
                 10 
                 •2H 2 O 
                 1 eq 
                 pre- 
                  3 × 100 
                 22-40 
                 54 
               
               
                 SBH to 
                   
                   
                   
                   
                   
                 formed 
               
               
                 NEt 3 HCl 
               
               
                   
               
             
          
         
       
     
     The results of additional experiments are summarized in the following table. 
     
       
         
               
               
               
               
               
               
               
             
               
               
               
               
               
               
               
               
               
             
           
               
                   
               
               
                   
                   
                 Mode of 
                   
                 conc. of 
                 Reaction 
                   
               
               
                 Borohydride 
                 MBH 4 , g 
                 addition 
                 Acid 
                 acid 
                 temperature 
                 yield 
               
               
                   
               
             
             
               
                   
               
             
          
           
               
                 NaBH 4 *2H 2 O 
                 10 
                   
                 acid 
                 HCl 
                 37 
                 wt % 
                 RT to 40° C. 
                 97 
               
               
                   
                   
                   
                 added 
               
               
                 NaBH 4 *2H 2 O 
                 10 
                   
                 performed 
                 HCl 
                 37 
                 wt % 
                 RT to 40° C. 
                 98 
               
               
                 NaBH 4 *2H 2 O 
                 10 
                   
                 acid 
                 H 2 SO 4   
                 98 
                 wt % 
                 RT to 40° C. 
                  0 
               
               
                   
                   
                   
                 added 
               
               
                 NaBH 4 *2H 2 O 
                 100 
                   
                 acid 
                 HCl 
                 37 
                 wt 
                 RT to 40° C. 
                 80 
               
               
                   
                   
                   
                 added 
               
               
                 NaBH 4 *2H 2 O 
                 50 
                   
                 acid 
                 HCl 
                 37 
                 wt 
                 RT to 40° C. 
                 74 
               
               
                   
                   
                   
                 added 
               
               
                 NaBH 4 *2H 2 O 
                 50 
                   
                 preformed 
                 HCl 
                 37 
                 wt 
                 RT to 40° C. 
                 85 
               
               
                 NaBH 4 *2H 2 O 
                 50 
                   
                 preformed 
                 HCl 
                 37 
                 wt 
                 8° C. to 20° C. 
                 64 
               
               
                 KBH 4   
                 12.25 
                   
                 acid 
                 HCl 
                 9.25 
                 wt % 
                 RT to 40° C. 
                 55 
               
               
                   
                   
                   
                 addition 
               
               
                 KBH 4   
                 12.25 
                   
                 acid 
                 HCl 
                 17.5 
                 wt % 
                 RT to 40° C. 
                 85 
               
               
                   
                   
                   
                 addition 
               
               
                 KBH 4   
                 12.25 
                   
                 acid 
                 HCl 
                 37 
                 wt % 
                 RT to 40° C. 
                 65 
               
               
                   
                   
                   
                 addition 
                   
                   
                   
                 (18 h) 
               
               
                 KBH 4   
                 12.25 
                   
                 acid 
                 HCl 
                 37 
                 wt % 
                 RT to 40° C. 
                 61 
               
               
                   
                   
                   
                 addition 
                   
                   
                   
                  (6 h) 
               
               
                 KBH 4   
                 12.25 
                   
                 acid 
                 H 2 SO 4   
                 75 
                 wt % 
                 RT to 40° C. 
                 79 
               
               
                   
                   
                   
                 addition 
               
               
                 KBH 4   
                 12.25 
                   
                 acid 
                 H 2 SO 4   
                 50 
                 wt % 
                 RT to 40° C. 
                 51 
               
               
                   
                   
                   
                 addition 
               
               
                 KBH 4   
                 12.25 
                 g 
                 acid 
                 H 2 SO 4   
                 25 
                 wt % 
                 RT to 40° C. 
                 44 
               
               
                   
                   
                   
                 addition 
               
               
                 Plant-made 
                 20 
                   
                 acid 
                 HCl 
                 37 
                 wt % 
                 RT to 35° C. 
                 68 
               
               
                 NaBH 4 *2H 2 O 
                   
                   
                 addition 
               
               
                 Plant-made 
                 20 
                   
                 preformed 
                 HCl 
                 37 
                 wt % 
                 RT to 35° C. 
                 62 
               
               
                 NaBH 4 *2H 2 O 
               
               
                 Synthetic 
                 20 
                   
                 preformed 
                 HCl 
                 37 
                 wt % 
                 RT to 35° C. 
                 71 
               
               
                 NaBH 4 *2H 2 O 
               
               
                   
               
               
                 RT = room temperature, i.e., 20-25° C.