22560-16-3

Basic information

• Product Name: LITHIUM TRIETHYLBOROHYDRIDE
• Synonyms: lithiumtriethylborohydride,calselect?lt,;lithiumtriethylborohydride,calselect?lt,intetrahydrofuran;SUPER-HYDRIDE(R);LITHIUM TRIETHYLBOROHYDRIDE;LITHIUM TRIETHYLHYDRIDOBORATE;LITHIUM TRIETHYLHYDROBORATE;super-hydride (lithium triethylboro-hydride;Lithium borohydride thiethyl
• CAS NO: 22560-16-3
• Molecular Formula: C₆H₁₆B*Li
• Molecular Weight: 105.94
• EINECS: 245-076-8
• Product Categories: NULL
• Mol File: 22560-16-3.mol

Chemical Properties

• Melting Point: 66-67° (Binger); mp 78-83° (dec) (Brown, 1977)
• Flash Point: 1 °F
• Appearance: Colorless to light gray/Liquid
• Density: 0.892 g/mL at 25 °C
• Storage Temp.: Flammables + water-Freezer (-20°C)e area
• Solubility: Miscible with tetrahydrofuran and benzene.
• Sensitive: Air & Moisture Sensitive
• Merck: 14,5544
• BRN: 4151240
• CAS DataBase Reference: LITHIUM TRIETHYLBOROHYDRIDE(CAS DataBase Reference)
• NIST Chemistry Reference: LITHIUM TRIETHYLBOROHYDRIDE(22560-16-3)
• EPA Substance Registry System: LITHIUM TRIETHYLBOROHYDRIDE(22560-16-3)

Safety Data

• Hazard Codes: F,C
• Statements: 11-14/15-19-34-40-37
• Safety Statements: 16-26-33-36/37/39-43-45
• RIDADR: UN 3399 4.3/PG 1
• WGK Germany: 1
• F: 10-23
• HazardClass: 4.3
• PackingGroup: I
• Hazardous Substances Data: 22560-16-3(Hazardous Substances Data)

Usage

Uses

Used in Organic Synthesis:
LITHIUM TRIETHYLBOROHYDRIDE is used as a powerful reducing agent for the conversion of carbonyl compounds to alcohols. It is particularly useful in the preparation of alkynyl alcohols from the cleavage of cyclic keto-vinyl triflates, the reduction of esters and lactones to alcohol and diol respectively, and the synthesis of 1-methylcyclohexanol and 1,4-butanediol from 1,2-epoxybutane and gamma-butyrolactone.
Used in Reagent Applications:
LITHIUM TRIETHYLBOROHYDRIDE is used as a reagent for various purposes, including:
1. Reducing alkyl halides to alkanes via dehydrogenation reactions.
2. The selective reduction of epoxides to Markovnikov alcohols.
3. Reducing tosylates or mesylates primary alcohols to hydrocarbons.
4. Reductive cyclization reactions for the preparation of useful intermediates.
5. Synthesis of hepta(manno-3-deoxy-6-O-t-butyldimethylsilyl)-β-cyclodextrin by reduction of hepta(manno-2,3-anhydro-6-O-t-butyldimethylsilyl)-β-cyclodextrin.
6. Hydrodefluorination of C-F bonds using a Ni catalyst.
7. Preparation of alkynyl alcohols from the cleavage of cyclic keto-vinyl triflates.
8. Stereoselective reduction of bicyclic imides, isoquinolines, and pyridines.
9. Preparation of tungsten and molybdenum hydride complexes.

Preparation

LiBHEt3 is prepared by the reaction of lithium hydride (LiH) and triethylborane (Et3B) in tetrahydrofuran (THF):LiH + Et3B → LiEt3BHIts THF solutions are stable indefinitely in the absence of moisture and air.

Precautions

Moisture sensitive. Air sensitive. Incompatible with water and strong oxidizing agents.

References

Tamang, S.; Kim, K.; Choi, H.; Kim, Y.; Jeong, S. Synthesis of colloidal InSb nanocrystals via in situ activation of InCl3. Dalton Trans. 2015, 44 (38), 16923-16928.Kandapallil, B.; Colborn, R. E.; Bonitatibus, P. J.; Johnson, F. Synthesis of high magnetization Fe and FeCo nanoparticles by high temperature chemical reduction. J. Magn. Magn. Mater. 2015, 378, 535-538.

InChI:InChI=1/C6H16B.Li/c1-4-7(5-2)6-3;/h7H,4-6H2,1-3H3;/q-1;+1

Synthetic route

triethyl borane (97-94-9) + lithium hydride → lithium triethylborohydride (22560-16-3)

Conditions	Yield
in an autoclave near 200°C;
in an autoclave near 200°C;
In tetrahydrofuran

triethyl borane (97-94-9) → lithium triethylborohydride (22560-16-3)

Conditions	Yield
With n-butyllithium In tetrahydrofuran; pentane byproducts: isobutylene; (N2); to stirred soln. of boranederiv. in THF was dropwise added pentane soln. of LiBu at -78°C, then mixt. was allowed to warm up to room temp.; not isolated, detected by (11)B-NMR;	>99

triethyl borane (97-94-9) + lithium tri-t-butoxyaluminum hydride → lithium triethylborohydride (22560-16-3)

Conditions	Yield
In tetrahydrofuran byproducts: Al{OC(CH3)3}; active intermediate;
In tetrahydrofuran byproducts: Al{OC(CH3)3}; active intermediate;

sodium triethylborohydride → lithium triethylborohydride (22560-16-3)

Conditions	Yield
Multi-step reaction with 2 steps 2: tetrahydrofuran View Scheme
Multi-step reaction with 2 steps 2: tetrahydrofuran View Scheme

{CH3N(PF2)2}3Co2(CO)2 (64799-21-9) + lithium triethylborohydride (22560-16-3) → {{CH3N(PF2)2}3Co2(CO)(CHO)}(1-)

Conditions	Yield
In tetrahydrofuran reduction with excess LiEt3BH at -78°C; not isolated; various yields for various conditions.;	100%

(η(6)-3-ethylanisole)tricarbonylchromium (88729-81-1) + lithium triethylborohydride (22560-16-3) → (ethylbenzene)tricarbonylchromium (12203-31-5)

Conditions	Yield
With chlorhydric or trifluoroacetic acid In tetrahydrofuran N2-atmosphere; refluxing (2 h), acid addn.; extg. (Et2O), washing (satd. Na2CO3 soln., brine), drying (Na2SO4), filtering, evapn. (reduced pressure), recrystn. (hexane / Me2CO);	100%

tris(triphenylphosphine)ruthenium(II) chloride (15529-49-4, 41756-81-4) + lithium triethylborohydride (22560-16-3) → hydridochlorotris(triphenylphosphine)ruthenium(II) (55102-19-7)

Conditions	Yield
In tetrahydrofuran IR;	100%
In tetrahydrofuran; toluene (N2); stirred at room temp. for 30 min; concd.; ethanol added; cooled to -20°C; filtered; washed (ethanol and petroleum ether); dried in vacuo; NMR;	>99

bis(1'-mesitylthiolatoferrocenyl)disulfane (326887-77-8) + lithium triethylborohydride (22560-16-3) → lithium 1'-(mesitylthio)ferrocene-1-thiolate

Conditions	Yield
In tetrahydrofuran mixed, stirred for 1,5 h; not isolated;	100%

(η(5):η(5)-(C5H3CO2Me)2)Mo2(CO)6 (184488-45-7, 184243-69-4) + lithium triethylborohydride (22560-16-3) → Li2(trans-1,1'-[η5:η5-(C5H3CO2Me)2]Mo2(CO)6)

Conditions	Yield
In tetrahydrofuran byproducts: Et3B; 0°C; evapn. (vac.);	100%

(CH3C(CH2P(C6H5)2)3)Re(CO)2(1+)*BF4(1-)=[(CH3C(CH2P(C6H5)2)3)Re(CO)2]BF4 (166989-37-3) + lithium triethylborohydride (22560-16-3) → (CH3C(CH2P(C6H5)2)3)Re(CO)2(H) (166989-33-9)

Conditions	Yield
In tetrahydrofuran; tetrahydrofuran-d8 N2-atmosphere; detd. by NMR spectroscopy;	100%

tricarbonyl[η(6)-2-chloro(trimethylsilyl)benzene]chromium + lithium triethylborohydride (22560-16-3) → tricarbonyl[η(6)-4-deuterio(trimethylsilyl)benzene]chromium (138496-16-9)

Conditions	Yield
With CF3COOH In tetrahydrofuran N2-atmosphere; stirring (-78°C, 50 min), CF3COOH addn.;	100%

C41H49Cl2FeNOP2 + lithium triethylborohydride (22560-16-3) → C41H50ClFeNOP2

Conditions	Yield
In tetrahydrofuran at -30 - 28℃; Schlenk technique; Inert atmosphere; Glovebox;	100%

C29H37Cl2FeNOP2 + lithium triethylborohydride (22560-16-3) → C29H38ClFeNOP2

Conditions	Yield
In tetrahydrofuran at -30 - 28℃; Schlenk technique; Inert atmosphere; Glovebox;	100%

C26H39Cl2FeNOP2 + lithium triethylborohydride (22560-16-3) → C26H40ClFeNOP2

Conditions	Yield
In tetrahydrofuran at -30 - 28℃; Schlenk technique; Inert atmosphere; Glovebox;	100%

[bis(2-diphenylphosphinophenyl)amide]PdCl + lithium triethylborohydride (22560-16-3) → C36H29NP2Pd

Conditions	Yield
In tetrahydrofuran; benzene-d6 for 0.166667h; Inert atmosphere;	100%

nido-NB10H13 + N,N,N,N,-tetramethylethylenediamine (110-18-9) + lithium triethylborohydride (22560-16-3) → Li(1+)*2(CH3)2N(CH2)2N(CH3)2*{NB10H12}(1-)={Li((CH3)2N(CH2)2N(CH3)2)2}{NB10H12}

Conditions	Yield
In tetrahydrofuran byproducts: B(C2H5)3, H2; addn. of Li(BHEt3) in THF to soln. of the borane at -78°C, stirred for 5 min at room temp., volatiles removed in vac., addn. of THF, addn. of tmeda;; concentrated, washed three times with pentane, dried;;	99%

6-azido-8,9:9,10-di-μ-hydro-1,2,3,4,5,7,7,8,9,10-decahydro-5,6-μ-amino-nido-decaborane + N,N,N,N,-tetramethylethylenediamine (110-18-9) + lithium triethylborohydride (22560-16-3) → Li(tmeda)2(1+)-{9-azido-3,4:3,8-di-μ-hydro-undecahydro-2-aza-1,5-didebor-closo-tridecaborate(1-)}

Conditions	Yield
In tetrahydrofuran; dichloromethane addn. of LiBHEt3 in THF to B-compd. in THF (0°C), stirring (15 min, room temp.), removal of volatiles (vac.), dissolution (CH2Cl2), addn. of org. compd. in CH2Cl2; reprecipitated with CH2Cl2, layered with hexane;	99%

Ir(CF3)Cl(CH3CN)(CO)[P(C6H5)3]2(1+)*SbF6(1-)=[Ir(CF3)Cl(CH3CN)(CO)(P(C6H5)3)2](SbF6) (105250-39-3) + lithium triethylborohydride (22560-16-3) → Ir(CF3)HCl(CO)[P(C6H5)3]2 (131100-72-6, 105250-42-8)

Conditions	Yield
In tetrahydrofuran addn. of 1 equiv. LiEt3BH in THF to stirred soln. of Ir-complex in THF (under N2); addn. of n-hexane, evapn. (reduced pressure), grey solid dissolved in CH2Cl2, filtered, crystn. (CH2Cl2/EtOH), elem. anal.;	99%

tetrachlorosilane (10026-04-7, 53609-55-5) + (μ-dithio)bis(tricarbonyliron) (14243-23-3) + lithium triethylborohydride (22560-16-3) → Si[S2Fe2(CO)6]2 (71592-21-7)

Conditions

Yield

In tetrahydrofuran under N2, to the stirred soln. of 2.91 mmol Fe compd. in THF cooled to -78°C was added LiEt3BH in THF in small portions, to this was added SiCl4 over 3 min at -78°C, mixt. was warmed to room temp.; volatiles were removed in vac., solid extd. 4 times with CH2Cl2, filtered under N2 through a Celite pad supporteed on a fritted funnel, solventremoved in vac., recrystd. from CH2Cl2, elem. anal.;

99%

[(CpCr(CO)2)2(μ,η(2)-P2)] + lithium triethylborohydride (22560-16-3) → [(CpCr(CO)2)2(μ-PH2)(μ-H)] (239134-51-1)

Conditions	Yield
In tetrahydrofuran Ar-atmosphere; excess hydride;	99%

Fe2(CO)6(μ-SNMe) (88253-22-9) + lithium triethylborohydride (22560-16-3) + trifluoroacetic acid (76-05-1) → Fe2(CO)6(μ-NHMe)(μ-SH)

Conditions	Yield
In tetrahydrofuran byproducts: Et2BO2CCF3, C2H6, CF3COO(1-); Ar-atmosphere; addn. of 2 equiv. of B-compd. to Fe-complex soln. at -78°C, addn. of excess CF3COOH, warming to room temp.; solvent removal (vac.), extn. into hexane, evapn.;	99%

1-(tert-butyldimethylsilyl)-2-chloro-1,2-dihydro-1,2-azaborinine (1138164-75-6) + lithium triethylborohydride (22560-16-3) → C4H4B(H)N(tert-butyldimethylsilyl) (1138164-76-7)

Conditions	Yield
In not given	99%

tetrahydrofuran (109-99-9) + C38H41ClIrOP*0.5CH2Cl2 + lithium triethylborohydride (22560-16-3) → C50H67IrLiO4P

Conditions	Yield
at -230℃; for 0.166667h; Inert atmosphere;	99%

lithium triethylborohydride (22560-16-3) + 17O-water (13968-48-4) → Li(17)OH

Conditions	Yield
In tetrahydrofuran byproducts: B(C2H5)3, H2; stirring stoich. amt. of H2(17)O and B-compd. in THF for 0.5 h at ca -5°C, then allowed to warm to room temp., stirred for 1 h, then under N2, solvent removed, solid heated to 100°C for 1 h, then at 250°C for 24 h at 1E-3 torr;	98%

{manganese(carbonyl)5(COPh)} + lithium triethylborohydride (22560-16-3) → Li(1+)*Mn(CO)4(CHO)(COC6H5)(1-)=Li[Mn(CO)4(CHO)(COC6H5)]

Conditions	Yield
With 1,2,4,5-tetrachlorobenzene In tetrahydrofuran byproducts: (C2H5)3B; NMR tube was dried at 110°C for 30 min, rinsed with Li(C2H5)3BH and THF, flushed with N2, sealed, a soln. of Mn-complex and 1,2,4,5-tetrachlorobenzene in THF was syringed, cooled to -50°C, a soln. of Li(C2H5)3BH in THF was added; monitored by NMR (1)H;	98%

(μ-dithio)bis(tricarbonyliron) (14243-23-3) + lithium triethylborohydride (22560-16-3) + dichlorodimethylgermanium (1529-48-2) → ((CH3)2GeS2)Fe2(CO)6 (74438-41-8)

Conditions	Yield
In tetrahydrofuran under N2, to the stirred soln. of 2.91 mmol Fe compd. in THF cooled to -78°C was added LiEt3BH in THF in portions, to this was added Me2GeCl2 at -78°C, warmed to room temp.; solvent evapd., chromy. (silicic acid-CH2Cl2), recrystd. from pentane, elem. anal.;	98%

Fe(η3:η2-indenide)(1,2-bis(diethylphosphino)ethane)Br + lithium triethylborohydride (22560-16-3) → Fe(η3:η2-indenide)(1,2-bis(diethylphosphino)ethane)H

Conditions	Yield
In tetrahydrofuran at -78 - 20℃; for 2h; Schlenk technique; Inert atmosphere;	98%

Pd(Cl)N(C6H4P(CH(CH3)2)2)2 (779333-78-7) + lithium triethylborohydride (22560-16-3) → C24H37NP2Pd

Conditions	Yield
In tetrahydrofuran at -35 - 20℃; for 1h; Inert atmosphere;	98%

(4,5-bis(diisopropylphosphino)-2,7,9,9-tetramethyl-9H-acridin-10-ide)NiCl + lithium triethylborohydride (22560-16-3) → (4,5-bis(diisopropylphosphino)-2,7,9,9-tetramethyl-9H-acridin-10-ide)NiH

Conditions	Yield
In tetrahydrofuran; benzene for 10h; Inert atmosphere;	97.1%

(benzene)tricarbonylchromium (697302-50-4, 697302-51-5, 12082-08-5, 697302-53-7) + lithium triethylborohydride (22560-16-3) → Li{(η5-cyclohexadienyl)tricarbonylchromium}

Conditions	Yield
In tetrahydrofuran N2-atmosphere;	97%

Fe(η-C5H5)(CO)2(COMe) + lithium triethylborohydride (22560-16-3) → Li(1+)*Fe(C5H5)(CO)(CHO)(COCH3)(1-)=Li[Fe(C5H5)(CO)(CHO)(COCH3)]

Conditions	Yield
With 1,2,4,5-tetrachlorobenzene In tetrahydrofuran byproducts: (C2H5)3B; NMR tube was dried at 110°C for 30 min, rinsed with Li(C2H5)3BH and THF, flushed with N2, sealed, a soln. of Fe-complex and 1,2,4,5-tetrachlorobenzene in THF was syringed, cooled to -50°C, a soln. of Li(C2H5)3BH in THF was added; monitored by NMR (1)H;	97%

(μ-dithio)bis(tricarbonyliron) (14243-23-3) + lithium triethylborohydride (22560-16-3) + ethyl iodide (75-03-6) → Fe2(CO)6(μ-SEt)2

Conditions	Yield
In tetrahydrofuran under N2, to the stirred soln. of 2.91 mmol Fe compd. in THF cooled to -78°C was added LiEt3BH in THF in small portions, to this was added EtI, mixt. stirred for 1 h; solvent evapd., chromy. (silicic acid-10% CH2Cl2/pentane) (a,e isomer/e,e isomer: 2.7);	96%

{RuCl2(H2C(C3H3N2)2)(C8H12)} (152391-10-1) + lithium triethylborohydride (22560-16-3) → {RuCl(H)(H2C(C3H3N2)2)(C8H12)} (152391-12-3)

Conditions	Yield
In tetrahydrofuran (N2; Schlenk-tube technique); a soln. of LiB(C2H5)3H in THF is added to a THF soln. of Ru complex at -78°C; stirring; allowing to warm to room temp. for 1h; pptn.;; filtration; washing with diethyl ether; elem. anal.;;	96%

[Fe(η(5)-C5H5)(CO)2(C(O)-p-C6H4OMe)] + lithium triethylborohydride (22560-16-3) → Li(1+)*Fe(C5H5)(CO)(CHO)(COC6H4OCH3)(1-)=Li[Fe(C5H5)(CO)(CHO)(COC6H4OCH3)]

Conditions	Yield
With 1,2,4,5-tetrachlorobenzene In tetrahydrofuran NMR tube was dried at 110°C for 30 min, rinsed with Li(C2H5)3BH and THF, flushed with N2, sealed, a soln. of Fe-complex and 1,2,4,5-tetrachlorobenzene in THF was syringed, cooled to -50°C, a soln. of Li(C2H5)3BH in THF was added; monitored by NMR (1)H;	96%

Upstream product

• 97-94-9 triethyl borane 

Downstream Products

• 132336-05-1 [2-(4-Bromo-phenyl)-ethyl]-ethyl-amine 
• 7439-89-6 iron 
• 97-94-9 triethyl borane 
• 121846-71-7 [Mn₂(CO)6(S₂CHP(C₆H₁₁)3)2] 
• 112490-02-5 OsH₂(PH₃)(CO)(PPh₃)2 
• 123239-21-4 {(P(C₆H₅)2N(CH₂)3N(CH₃)(CH₂)3NP(C₆H₅)2)Mo(CO)4(C₄H₈OLi)}^(1-)*Li⁽¹⁺⁾*(x)C₄H₈O 
• 125873-85-0 (S)-pinanediol {(1S,2R)-2,3-bis(benzyloxy)propyl}boronate-1-d 

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ADDITION COMPOUNDS OF ALKALI METAL HYDRIDES XVIII. REACTION OF TRIALKYLBORANES WITH t-BUTYLLITHIUM. A GENERAL CONVENIENT METHOD FOR THE PREPARATION OF LITHIUM TRIALKYBOROHYDRIDES

The reaction of t-butyllithium with representative trialkylboranes possessing widely differing steric requirements was examined.This reaction occurs rapidly in ether solvents, even at -78 deg C, with formation of the corresponding lithium trialkylborohydride in quantitative yield.This synthesis is highly general, accomodating even strongly hindered trialkylboranes such as tris(trans-2-methylcyclopentyl)borane and trisiamylborane.The only by-product is isobutylene, which is generally innocuous and easily removed.The lithium trialkylborohydrides were characterized byhydride analyses, infrared spectra, and 11B NMR spectra.The formation of the trialkylborohydrides appears to be due to kinetic, rather than thermodynamic, factors.This reaction provides a highly general, facile, and quantitative route to the lithium trialkylborohydrides.