Thermolysis of tetraalkylammonium borohydrides to bis(tetraalkylammonium) decahydrodecaboranes

• US 4,391,993 A
• Filed: 02/12/1982
• Issued: 07/05/1983
• Est. Priority Date: 02/12/1982
• Status: Expired due to Fees

• Current Assignee: United States Of America As Represented By The Secretary Of The Army (Government of the United States of America)
• Original Assignee: The United States Of America As Represented By The Secretary Of The Army
• Inventors: Sayles, David C.
• Primary Examiner(s): SNEED, HELEN
• Application Number:
  US06/348,538
• Time in Patent Office: 508 Days
• Field of Search: 568/3, 568/4, 422/130, 422/205, 422/202, 422/225
• US Class Current: 568/4
• CPC Class Codes: C07F 5/00 Compounds containing elements of Groups 3 or 13 of the Periodic Table
• CPC Class Codes: C07F 5/022 without C-boron linkages

Abstract

Disclosed is an improved method and the thermolysis equipment setup for certing tetraethylammonium tetrahydridoborane to bis(tetraethylammonium) decahydrodecaborane by a thermolysis reaction which increases the yield in the range between about 22% to 64%, and, perhaps higher. The heat transfer control is maintained by employing triethylamine borane in the reaction mixture between about 175° C. and 186° C. for a reaction time from about 1 hour to about 2.5 hours. The disclosed thermolysis procedure is successful in dissipating a major portion of the exothermic heat. The control of the generated heat serves to minimize the formation of the byproduct bis(tetraethylammonium) dodecahydrododecaborane while increasing the yield of the desired product, bis(tetraethylammonium) decahydrodecaborane.

Claims

1. A process for the thermolysis reaction of tetraethylammonium borohydride to yield bis(tetraalkylammonium) decahydrodecaborane which comprises:

(i) combining Et₄ NBH₄ in a mole ratio from about 0.3 to 1.0 with a boron-based solvent Et₄ NBH₃ in a mole ratio from about 0.2 to 4.0 to form a reaction mixture, (wherein Et is C₂ H₅), in a thermolysis reactor vessel having a plurality of outlets for various functions including an outlet for the introduction of reactants and an inert gas, an outlet through which the reaction temperature is monitored, and an outlet for discharging reaction products to a recovery system, said reactor vessel provided with an immersion oil heating means for heating including a temperature control means for controlling the reaction temperature, a means for maintaining an inert atmosphere of nitrogen over said reaction mixture, and a temperature measuring means for measuring temperature of the reaction mixture;

(ii) connecting one of said outlets of said reactor vessel to a recovery system comprised of a tube member having a heated tube section on one end to prevent any reflux action to said reaction vessel, and said tube member having an air-cooled condenser section on the other end of said tube member, said air-cooled condenser section being connected to a distillate receiver, said distillate receiver having a discharge outlet that is connected in series with a 0°

C. cooled trap, a -78°

C. cooled trap, a back pressure regulator, and a wet test gas meter;

said cooled traps for collecting the condensable gases and said wet test gas meter for measuring the non-condensable gases;

(iii) introducing and maintaining an inert atmosphere of nitrogen in said reactor vessel and said recovery system;

(iv) heating said reaction mixture while stirring and controlling said reacting mixture to maintain a thermolysis temperature between about 175°

C. and 186°

C. for a reaction time from about 1 to about 2.5 hours until chemical reaction ceases;

(v) removing said reactor vessel from said immersion oil heating means, and cooling the residue in said reactor vessel to room temperature;

(vi) filtering off any remaining triethylamine borane solvent and recovering the filter cake;

(vii) washing said filter cake with hexane to remove any additional triethylamine borane; and

(viii) drying said washed filter cake to remove any hexane adhering to said filter cake to yield (Et₄ N)₂ B₁₀ H₁₀.

2. The process as set forth in claim 1 wherein said Et₄ NBH₄ is reacted in said Et₃ NBH₃ solvent in a mole ratio of about 0.345 of said Et₄ NBH₄ to about 0.87 of said Et₃ NBH₃ and wherein said thermolysis temperature is maintained between about 175°

C. and 186°

C. for a reaction time of about 1-2 hours to yield said (Et₄ N)₂ B₁₀ H₁₀ in a percent yield of about 31.

3. The process, as set forth in claim 1, wherein said Et₄ BNH₄ is reacted in said Et₃ NBH₃ solvent in a mole ratio of about 0.345 of said Et₄ NBH₄ to about 1.067 of said Et₃ NBH₃, and wherein thermolysis temperature is maintained at about 183°

C. for a reaction time of about 1.5 hours to yield said (Et₄ N)₂ B₁₀ H₁₀ in a percent yield of about 34.

4. The process, as set forth in claim 1, wherein said Et₄ NBH₄ is reacted in said Et₃ NBH₃ solvent in a mole ratio of about 0.345 of said Et₄ NBH₄ to about 0.6 of said Et₃ NBH₃, and wherein said thermolysis temperature is maintained at about 183°

C. for a reaction time of about 1.5 hours to yield said (Et₄ N)₂ B₁₀ H₁₀ in a percent yield of about 36.

5. The process, as set forth in claim 1, wherein said Et₄ NBH₄ is reacted in said Et₃ NBH₃ solvent in a mole ratio of about 0.345 of said Et₄ NBH₄ to about 0.217 of said Et₃ NBH₃, and wherein thermolysis temperature is maintained at about 186°

C. for a reaction time of about 2.5 hours to yield said (Et₄ N)₂ B₁₀ H₁₀ in a percent yield of about 64.