STABILIZED DEUTEROBORANE-TETRAHYDROFURAN COMPLEX

• US 20070197695A1
• Filed: 02/08/2007
• Published: 08/23/2007
• Est. Priority Date: 02/10/2006
• Status: Active Grant

• Current Assignee: Sigma-Aldrich Company (Sigma-Aldrich Corporation)
• Original Assignee: Sigma-Aldrich Company (Sigma-Aldrich Corporation)
• Inventors: Todd, Robert, Gao, Peng, Hewitt, Christopher, Potyen, Mark, Josyula, Kanth
• Granted Patent: US 7,750,168 B2
• Time in Patent Office: Days
• US Class Current: 524/110
• CPC Class Codes: C08K 5/0091 Complexes with metal-heteroatom-bonds
• CPC Class Codes: C08K 5/55 Boron-containing compounds C08K5/0091 takes precedence

Abstract

A stabilized deuteroborane-tetrahydrofuran complex is disclosed. Also disclosed are processes for the preparation of the deuteroborane-tetrahydrofuran complex and methods of storing and transporting the prepared complex. The deuteroborane-tetrahydrofuran complexes exhibit enhanced shelf life and increased self-accelerated decomposition temperatures.

Claims

1. A composition comprising

(a) a deuteroborane-tetrahydrofuran complex, (b) tetrahydrofuran and (c) a stabilizer wherein:

(i) the stabilizer is selected from the group consisting of amines, sulfides, phosphines, aminoborohydrides, borates, and combinations thereof,

(ii) the concentration of the deuteroborane-tetrahydrofuran complex in the composition is at least about 0.5 moles per liter,

(iii) the molar ratio of the deuteroborane-tetrahydrofuran complex to the stabilizer is at least 10;

1, and

(iv) the deuteroborane is of the formula BD_yH_3-y wherein y is from 1 to 3.

4. The composition of claim 1 wherein y is 3.

5. The composition of claim 1 wherein the molar ratio of the deuteroborane-tetrahydrofuran complex to the stabilizer is from about 10:

1 to about 10000;

1.

6. The composition of claim 1 wherein the concentration of the deuteroborane-tetrahydrofuran complex is about 0.5 moles per liter to about 2.5 moles per liter.

7. The composition of claim 1 wherein the amine stabilizer is of formula (Ia), formula (Ib) or formula (Ic):

8. The composition of claim 7 wherein

R₁ is selected from the group consisting of hydrogen, methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, t-butyl, sec-butyl, t-octyl, ethyl ether, ethyl methyl ether, methylallyl, phenyl and trimethylsilyl, and

R₂ and R₃ are independently selected from the group consisting of methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, t-butyl, sec-butyl, t-octyl, ethyl ether, ethyl methyl ether, methylallyl, phenyl and trimethylsilyl.

9. The composition of claim 1 wherein the amine stabilizer is a metal amide of formula (Id):

R₁R₂N⁻

M⁺ 

 

(Id)

wherein

R₁ and R² are independently selected from hydrogen, phenyl, straight or branched chain alkyl, alkene or alkoxy having 1 to 8 carbon atoms, cycloalkyl having 3 to 8 carbon atoms, and silyl tri-substituted with substituents independently selected from hydrogen, phenyl, and straight or branched chain alkyl, alkene or alkoxy having 1 to 8 carbon atoms, and

M⁺ is a metal counterion.

10. The composition of claim 9 wherein

R₁ and R₂ are independently selected from the group consisting of methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, t-butyl, sec-butyl, t-octyl, ethyl ether, ethyl methyl ether, methylallyl, phenyl and trimethylsilyl, and

M⁺ is selected from sodium, potassium and lithium.

11. The composition of claim 1 wherein the amine stabilizer comprises a heterocycle corresponding to formula (II):

12. The composition of claim 11 wherein the heterocycle of formula (II) is selected from substituted or unsubstituted piperidine, piperazine, pyridine, pyrazine, pyridazine and pyrimidine.

13. The composition of claim 1 wherein the amine stabilizer is a heterocycle corresponding to formula (III):

14. The composition of claim 13 wherein the heterocycle of formula (III) is selected from substituted or unsubstituted 1H-Pyrrole, pyrrolidine, 3-pyrroline, imidazole, pyrazole, 2-pyrazoline and triazole.

15. The composition of claim 11 or claim 13 wherein the heterocycle contains one nitrogen heteroatom and a sulfur or oxygen heteroatom.

16. The composition of claim 1 wherein the aminoborohydride is of formula (VI):

R₁R₂NBH₃⁻

M⁺ 

 

(VI)

wherein

R₁ and R₂ are independently selected from straight or branched chain alkyl, alkene or alkoxy having 1 to 8 carbon atoms, and cycloalkyl having 3 to 8 carbon atoms, and M⁺ is a metal cation selected from lithium, sodium and potassium.

17. The composition of claim 1 wherein the phosphine is of formula (VIII):

18. The composition of claim 17 wherein the cycloalkyl is selected from cyclopentyl and cyclohexyl, and the phenyl is selected from xylyl and tolyl.

19. The composition of claim 17 wherein any two of R₆-R₈ and the phosphorus atom form a substituted or unsubstituted heterocycle containing from 3 to 8 atoms.

20. The composition of claim 1 wherein the borate is of formulae (XI) or (XII):

21. The composition of claim 1 wherein the stabilizer is supported

on at least a portion of the surface of a polymer matrix or an inert carrier,

in at least a portion of an internal matrix or pores of a polymer matrix or an inert carrier, or

on at least a portion of the surface and at least a portion of the internal matrix or pores of a polymer matrix or an inert carrier

wherein the polymer matrix or inert carrier are immersed in the composition.

22. The composition of claim 21 wherein the inert carrier is selected from titanium dioxide, silicone dioxide, alumina, carbon and zeolite.

23. The composition of claim 21 wherein the polymer is selected from polyolefin, polyvinyl chloride, nitrile, polyethylene terephthalate, polyurethane, polystyrene, polytetrafluoroethylene, silicone rubber and polyvinylidene chloride.

24. The composition of claim 1 wherein the composition is a solution.

2. (canceled)

3. A method of storing a composition containing at least about 0.5 moles per liter of a deuteroborane-tetrahydrofuran complex in a solvent system comprising tetrahydrofuran, the method comprising

sealing a container having a storage volume of at least 0.10 liters, the sealed container containing a liquid in the storage volume, the liquid comprising tetrahydrofuran, the deuteroborane-tetrahydrofuran complex, and a stabilizer selected from the group consisting of amines, sulfides, phosphines, aminoborohydrides, borates, and combinations thereof

wherein the molar ratio of the deuteroborane-tetrahydrofuran complex to the stabilizer is at least 10:

1 and the deuteroborane is of the formula BD_yH_3-y wherein y is from 1 to 3.

32. The method of claim 3 wherein y is 3.

33. The method of claim 3 wherein the molar ratio of the deuteroborane-tetrahydrofuran complex to the stabilizer is from about 10:

1 to about 10000;

1.

25. (canceled)

26. (canceled)

27. A method of storing and transporting a composition comprising at least about 0.5 moles per liter of a deuteroborane-tetrahydrofuran complex in a solvent system containing tetrahydrofuran, the method comprising sealing the composition in a container, the sealed container comprising the composition, a gas, and a gas-solution interface

wherein the ratio of the surface area of the gas-solution interface to the volume of the composition in the sealed container is about 2 cm² per liter to about 200 cm² per liter and the deuteroborane is of the formula BD_yH_3-y wherein y is from 1 to 3.

28. The method of claim 27 wherein y is 3.

29-31. -31. (canceled)