Tetrabutylammonium borohydride
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| Names | |
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| IUPAC name
Tetrabutylammonium tetrahydroborate | |
Other names
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| Identifiers | |
3D model (JSmol) |
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| ChemSpider | |
| ECHA InfoCard | 100.046.948 |
| EC Number |
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PubChem CID |
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CompTox Dashboard (EPA) |
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| Properties | |
| C16H40BN | |
| Molar mass | 257.31 g·mol−1 |
| Appearance | White to off-white crystalline solid |
| Density | 0.92 g/cm3 |
| Melting point | 123–126 °C (253–259 °F; 396–399 K) |
| insoluble | |
| Solubility | soluble in CH2Cl2, CHCl3, THF, ethyl acetate, toluene |
| Hazards | |
| GHS labelling:[1] | |
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| Danger | |
| H261, H314 | |
| P231+P232, P260, P264, P280, P301+P330+P331, P302+P361+P354, P304+P340, P305+P354+P338, P316, P321, P363, P370+P378, P402+P404, P405, P501 | |
| Related compounds | |
Other anions |
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Other cations |
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Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
Infobox references | |
Tetrabutylammonium borohydride (abbreviated as TBABH or n-Bu4NBH4) is a quaternary ammonium salt with the chemical formula [(C4H9)4N]+[BH4]−. It is an organic-soluble hydride reagent primarily used as a reducing agent in organic chemistry.[2]
Unlike alkali metal borohydrides such as sodium borohydride (NaBH4) or lithium borohydride (LiBH4), the bulky lipophilic tetrabutylammonium cation allows this compound to dissolve readily in non-polar and non-protic organic solvents.
Properties
Tetrabutylammonium borohydride is a white to off-white crystalline solid. It is stable under ambient conditions but should be stored in a dry environment due to its mild sensitivity to moisture over extended periods.[3]
Its primary advantage over conventional borohydrides is its solubility in halogenated solvents (such as dichloromethane and chloroform) and ethereal solvents (such as tetrahydrofuran), in which inorganic borohydrides are largely insoluble.[2]
Synthesis
Tetrabutylammonium borohydride is typically prepared via a salt metathesis reaction between tetrabutylammonium bromide (TBAB) or tetrabutylammonium hydroxide and sodium borohydride in an organic solvent or aqueous-organic biphasic system:
- [(C4H9)4N]Br + NaBH4 → [(C4H9)4N]BH4 + NaBr
The precipitated inorganic salt (NaBr) is filtered off, and the product is isolated by recrystallization.
Applications
Organic reductions
TBABH is widely utilized in organic synthesis for the selective reduction of various functional groups under mild, anhydrous conditions:
- Aldehydes and ketones: Reduces carbonyl compounds smoothly into primary and secondary alcohols.[2]
- Halogenated solvent Activation: When used in dichloromethane (CH2Cl2), the solvent can provide mild electrophilic activation, enhancing the rate of carbonyl reduction compared to reactions in less polar non-protic solvents.[2]
- Selective reductions: Capable of selectively reducing imines, acid chlorides, oximes, and quaternary ammonium or iminium ions without affecting more resistant functional groups like esters or amides.[4]
- Radical anion formation: Electron transfer from the borohydride ion to unsaturated organic substrates under photoinduced or thermal conditions can generate radical anion intermediates.[5]
Phase-transfer chemistry
Because of its high solubility in organic phases and quaternary ammonium structure, TBABH can function in phase-transfer catalysis setups, allowing reduction reactions to take place across biphasic media without the need for protic co-solvents.
See also
References
- ↑ PubChem. "Tetrabutylammonium borohydride". pubchem.ncbi.nlm.nih.gov. Retrieved 2026-08-19.
- 1 2 3 4 Raber, D. J.; Guida, W. C. (1976). "Tetrabutylammonium Borohydride. Borohydride Reductions in Dichloromethane". The Journal of Organic Chemistry. 41 (4): 690–696. doi:10.1021/jo00866a022.
- ↑ Jaroń, Tomasz (2023). "The Preparation, Characterization, and Pressure-Influenced Dihydrogen Interactions of Tetramethylphosphonium Borohydride". Materials. 16 (15): 5334. Bibcode:2023Mate...16.5334J. doi:10.3390/ma16155334. PMC 10420206. PMID 37570038.
- ↑ Kaufmann, D. E.; Matteson, D. S.; Schaumann, E.; Regitz, M., eds. (2005). "Product Subclass 2: Borohydrides". Science of Synthesis: Houben-Weyl Methods of Molecular Transformations. Vol. 6. Georg Thieme Verlag. doi:10.1055/sos-SD-006-00052. ISBN 978-3-13-112191-2.
- ↑ Lucarini, Marco; Pedulli, Gian Franco; Alberti, Angelo; Paradisi, Carmen; Roffia, Sergio (1993). "Spontaneous and photoinduced formation of radical anions in the reaction of borohydrides with unsaturated compounds". Journal of the Chemical Society, Perkin Transactions 2 (11): 2083–2088. doi:10.1039/P29930002083.