Triethylborane Explained

Triethylborane (TEB), also called triethylboron, is an organoborane (a compound with a B–C bond). It is a colorless pyrophoric liquid. Its chemical formula is or, abbreviated . It is soluble in organic solvents tetrahydrofuran and hexane.

Preparation and structure

Triethylborane is prepared by the reaction of trimethyl borate with triethylaluminium:

Et3Al + (MeO)3B → Et3B + (MeO)3AlThe molecule is monomeric, unlike H3B and Et3Al, which tend to dimerize. It has a planar BC3 core.

Applications

Turbojet engines

Triethylborane was used to ignite the JP-7 fuel in the Pratt & Whitney J58 turbojet/ramjet engines powering the Lockheed SR-71 Blackbird[1] and its predecessor, the A-12 OXCART. Triethylborane is suitable because it ignites readily upon exposure to oxygen. It was chosen as an ignition method for reliability reasons, and in the case of the Blackbird, because JP-7 fuel has very low volatility and is difficult to ignite. Conventional ignition plugs posed a high risk of malfunction. Triethylborane was used to start each engine and to ignite the afterburners.[2]

Rocketry

Mixed with 10–15% triethylaluminium, it was used before lift-off to ignite the F-1 engines on the Saturn V rocket.[3]

The Merlin engines that power the SpaceX Falcon 9 rocket use a triethylaluminium-triethylborane mixture (TEA-TEB) as a first- and second-stage ignitor.[4]

The Firefly Aerospace Alpha launch vehicle's Reaver engines are also ignited by a triethylaluminium-triethylborane mixture.[5]

Organic chemistry

Industrially, triethylborane is used as an initiator in radical reactions, where it is effective even at low temperatures.[6] As an initiator, it can replace some organotin compounds.

It reacts with metal enolates, yielding enoxytriethylborates that can be alkylated at the α-carbon atom of the ketone more selectively than in its absence. For example, the enolate from treating cyclohexanone with potassium hydride produces 2-allylcyclohexanone in 90% yield when triethylborane is present. Without it, the product mixture contains 43% of the mono-allylated product, 31% di-allylated cyclohexanones, and 28% unreacted starting material.[7] The choice of base and temperature influences whether the more or less stable enolate is produced, allowing control over the position of substituents. Starting from 2-methylcyclohexanone, reacting with potassium hydride and triethylborane in THF at room temperature leads to the more substituted (and more stable) enolate, whilst reaction at -78 °C with potassium hexamethyldisilazide, and triethylborane generates the less substituted (and less stable) enolate. After reaction with methyl iodide the former mixture gives 2,2-dimethylcyclohexanone in 90% yield while the latter produces 2,6-dimethylcyclohexanone in 93% yield.[8] The Et stands for ethyl group .

It is used in the Barton–McCombie deoxygenation reaction for deoxygenation of alcohols. In combination with lithium tri-tert-butoxyaluminum hydride it cleaves ethers. For example, THF is converted, after hydrolysis, to 1-butanol. It also promotes certain variants of the Reformatskii reaction.[9]

Triethylborane is the precursor to the reducing agents lithium triethylborohydride ("Superhydride") and sodium triethylborohydride.[10]

MH + Et3B → MBHEt3 (M = Li, Na)

Triethylborane reacts with methanol to form diethyl(methoxy)borane, which is used as the chelating agent in the Narasaka - Prasad reduction for the stereoselective generation of syn-1,3-diols from β-hydroxyketones.[11] [12]

Safety

Triethylborane is strongly pyrophoric, with an autoignition temperature of,[13] burning with an apple-green flame characteristic for boron compounds. Thus, it is typically handled and stored using air-free techniques. Triethylborane is also acutely toxic if swallowed, with an of 235 mg/kg in rat test subjects.[14]

See also

Notes and References

  1. Web site: Lockheed SR-71 Blackbird. 2009-05-05. March Field Air Museum. dead. https://web.archive.org/web/20000304181849/http://www.marchfield.org/sr71a.htm. 2000-03-04.
  2. Web site: Lockheed SR-71 Blackbird Flight Manual. 2011-01-26. www.sr-71.org. 2011-02-02. https://web.archive.org/web/20110202220020/http://www.sr-71.org/blackbird/manual/1/1-22.php. live.
  3. Book: 86. The Saturn V F-1 Engine: Powering Apollo Into History. A. Young. Springer. 2008. 978-0-387-09629-2.
  4. http://www.spaceflightnow.com/falcon9/001/status.html Mission Status Center, June 2, 2010, 1905 GMT
  5. Web site: https://twitter.com/Firefly_Space/status/1090319933534334977 . 2023-02-05 . Twitter . en.
  6. Encyclopedia: Robert J.. Brotherton. C. Joseph. Weber. Clarence R.. Guibert. John L.. Little. Boron Compounds. Ullmann's Encyclopedia of Industrial Chemistry. 15 June 2000. Wiley-VCH. 10.1002/14356007.a04_309. 3-527-30673-0.
  7. Book: https://books.google.com/books?id=JEcSmEKtoT4C&pg=PT1847. Handbook of Reagents for Organic Synthesis. 11. Reagents for Radical and Radical Ion Chemistry. Crich. David. 2008. John Wiley & Sons. 978-0-470-06536-5. Enoxytriethylborates and Enoxydiethylboranes. 2019-01-27. 2022-02-19. https://web.archive.org/web/20220219194543/https://books.google.com/books?id=JEcSmEKtoT4C&pg=PT1847. live.
  8. Highly regioselective generation of "thermodynamic" enolates and their direct characterization by NMR. Ei-ichi. Negishi. Ei-ichi Negishi. Sugata. Chatterjee. Tetrahedron Letters. 24. 13. 1983. 1341–1344. 10.1016/S0040-4039(00)81651-2.
  9. Encyclopedia: Yoshinori. Yamamoto. Takehiko. Yoshimitsu. John L.. Wood. John L. Wood. Laura Nicole. Schacherer. Triethylborane. Encyclopedia of Reagents for Organic Synthesis. 10.1002/047084289X.rt219.pub3. 15 March 2007. Wiley. 978-0-471-93623-7.
  10. Book: Binger. P.. Köster. R.. Sodium Triethylhydroborate, Sodium Tetraethylborate, and Sodium Triethyl-1-Propynylborate . Inorganic Syntheses. Inorganic Syntheses. 1974. 15. 136–141. 10.1002/9780470132463.ch31. 978-0-470-13246-3.
  11. A Novel Method for the In situ Generation of Alkoxydialkylboranes and Their Use in the Selective Preparation of 1,3-syn Diols. Chen. Kau-Ming. Gunderson. Karl G.. Hardtmann. Goetz E.. Prasad. Kapa. Repic. Oljan. Shapiro. Michael J.. Chemistry Letters. 1987. 16. 10. 1923–1926. free. 10.1246/cl.1987.1923.
  12. Book: Yang, Jaemoon. https://books.google.com/books?id=A_vUdr6ABGIC&pg=PA151. Diastereoselective Syn-Reduction of β-Hydroxy Ketones. Six-Membered Transition States in Organic Synthesis. 2008. John Wiley & Sons. 151–155. 978-0-470-19904-6. 2019-01-27. 2022-02-19. https://web.archive.org/web/20220219194529/https://books.google.com/books?id=A_vUdr6ABGIC&pg=PA151. live.
  13. Web site: Fuels and Chemicals - Autoignition Temperatures . 2017-08-26 . 2015-05-04 . https://web.archive.org/web/20150504022056/http://www.engineeringtoolbox.com/fuels-ignition-temperatures-d_171.html . live .
  14. Web site: Archived copy . 2020-09-26 . 2022-02-19 . https://web.archive.org/web/20220219194531/https://www.sigmaaldrich.com/US/en/sds/ALDRICH/257192 . live .