7397-43-5

Basic information

• Product Name: TRI-TERT-BUTYL BORATE
• Synonyms: Tri(1,1-dimethylethoxy)borane;Tri-tert-butyl borate,98%;Tri-tert-butyl borate,Boron tert-butoxide, Tri-tert-butoxyborane;Tri-tert-butyl borate 98%;Boric acid,tris(1,1-dimethylethyl) ester;boricacidtri-tert-butylester;BORON T-BUTOXIDE;TRI-TERT-BUTYL BORATE
• CAS NO: 7397-43-5
• Molecular Formula: C₁₂H₂₇BO₃
• Molecular Weight: 230.15
• Mol File: 7397-43-5.mol
• Article Data: 5

Chemical Properties

• Melting Point: 18-19 °C(lit.)
• Boiling Point: 101 °C74 mm Hg(lit.)
• Flash Point: 85 °F
• Appearance: Colorless/Liquid
• Density: 0.811 g/mL at 25 °C(lit.)
• Vapor Pressure: 1.55mmHg at 25°C
• Refractive Index: n20/D 1.389(lit.)
• Storage Temp.: Flammables area
• CAS DataBase Reference: TRI-TERT-BUTYL BORATE(CAS DataBase Reference)
• NIST Chemistry Reference: TRI-TERT-BUTYL BORATE(7397-43-5)
• EPA Substance Registry System: TRI-TERT-BUTYL BORATE(7397-43-5)

Safety Data

• Statements: 10
• Safety Statements: 16-33
• RIDADR: UN 1993 3/PG 3
• WGK Germany: 3
• TSCA: No
• HazardClass: 3.2
• PackingGroup: III
• Hazardous Substances Data: 7397-43-5(Hazardous Substances Data)

Usage

Chemical Properties

CLEAR COLOURLESS LIQUID

Uses

Tri-tert-butyl borate can be used as:An additive in the synthesis of chiral α-hydroxy esters by reacting dimethylzinc with α-ketoesters using (?)-2-exo-morpholinoisobornane-10-thiol.A starting material in the synthesis of boronate of (+)-pinane-2,3-diol.

General Description

Tri-tert-butyl borate is an organoborate commonly used to prepare other borate esters. It is also used as a substrate in Rh-catalyzed carbonylation reactions.

InChI:InChI=1/C12H27BO3/c1-10(2,3)14-13(15-11(4,5)6)16-12(7,8)9/h1-9H3

Synthetic route

tert-butyl alcohol (75-65-0) → tri-(tert-butyl)borate (7397-43-5)

Conditions	Yield
With pyridine; chloroform; boron trichloride
With pyridine; boron trichloride; pentane
With sodium borate; acetic acid anschliessendes Erhitzen;
With boric acid; benzene unter Abdestillieren des Wassers;
With boric acid; benzene unter Abdestillieren des Wassers;

boric acid (11113-50-1) + tert-butyl alcohol (75-65-0) → tri-(tert-butyl)borate (7397-43-5)

Conditions	Yield
With calcium hydride In neat (no solvent) byproducts: H2; react. under N2, slow addn. of the alcohol via syringe to B(OH)3 (ratio 3:1) and CaH2, cooling in a water bath, slow heating to 80-90°C for 24 h after abating the H2 gas evolution; distn. of the volatile products under reduced pressure (distn. pot temp. <= 120°C);	60%
In not given azeotropic distn. (reflux); distn., elem. anal.;

tert-butyl alcohol (75-65-0) + decaborane(14) → tri-(tert-butyl)borate (7397-43-5)

Conditions	Yield
With benzene

triethyl borate (150-46-9) + tert-butyl alcohol (75-65-0) → tri-(tert-butyl)borate (7397-43-5)

Conditions	Yield
With sodium unter Abdestillieren des Aethanols;

hafnium borohydride + tert-butyl alcohol (75-65-0) → tri-(tert-butyl)borate (7397-43-5) + tetrakis(2-methyl-2-propoxy)hafnium * bis(2-methyl-2-propoxy)borane

Conditions	Yield
In pentane byproducts: H2; (Ar (N2) or vac.); dropwise addn. of excess of t-C4H9OH to Hf-complex in pentane with stirring (50 min, room temp.); concn., filtration, drying (vac.); elem. anal.;	A n/a B 85%

zirconium(IV) borohydride + tert-butyl alcohol (75-65-0) → tri-(tert-butyl)borate (7397-43-5) + tetrakis(2-methyl-2-propoxy)zirconium * bis(2-methyl-2-propoxy)borane

Conditions	Yield
In pentane byproducts: H2; (Ar (N2) or vac.); dropwise addn. of excess of t-C4H9OH to Zr-complex in pentane with stirring (50 min, room temp.); concn., sepn. by filtration, a) drying (vac.), b) distn. of filtrate (vac.); elem. anal.;	A 55% B 71%

Trimethyl borate (121-43-7) + tert-butyl alcohol (75-65-0) → tri-(tert-butyl)borate (7397-43-5)

Conditions	Yield
unter Entfernen des entstehenden Methanols;

dimethylsulfide borane complex (13292-87-0) + tert-butyl alcohol (75-65-0) → tri-(tert-butyl)borate (7397-43-5)

Conditions	Yield
In neat (no solvent) byproducts: H2, S(CH3)2; react. in a round-bottom flask under N2, addn. of the alcohol to the borane complex at room temp. (stirred), refluxed (according to Brown, Krishnamurthy, J.Org.Chem. 1978, 43, 2731; with a slight modification); distn. from a small piece of K metal;

Bis(diethylamino)(trimethylstannyl)boran (79812-14-9) + tert-butyl alcohol (75-65-0) → tri-(tert-butyl)borate (7397-43-5) + tris(diethylamino)borane (867-97-0) + trimethylstannane (1631-73-8)

Conditions	Yield
equimolar amt. of educt, t-BuOH dropped to B(NEt2)2Sn(CH3)3 at -30°C, stirred;	A n/a B 90% C 96%

tris(dimethylamino)borane (4375-83-1) + tert-butyl alcohol (75-65-0) → tri-(tert-butyl)borate (7397-43-5)

Conditions	Yield
In neat (no solvent) molar ratio alcohol:borane=3:1;;	>90

tris(diethylamino)borane (867-97-0) + tert-butyl alcohol (75-65-0) → tri-(tert-butyl)borate (7397-43-5)

Conditions	Yield
In neat (no solvent) molar ratio alcohol:borane=3:1;;	>90

2-(dimethyl sulfide)-4,5-[1,2-dicarba-closo-dodecaborano(12)]-1,3-diselena-2-boracyclopentane (1240387-50-1) + tert-butyl alcohol (75-65-0) → tri-(tert-butyl)borate (7397-43-5) + 1,2-di(hydroseleno)-1,2-dicarba-closo-dodecaborane(12) (325820-04-0)

Conditions	Yield
In (2)H8-toluene (inert atm.); addn. of tert-butanol to suspn. of Se compd. in toluene-d8at -30°C, heating to 40°C for 30 min; evapn. in vac.;

borane tetrahydrofuran + lithium tert-butoxide (1907-33-1) → lithium borohydride + tri-(tert-butyl)borate (7397-43-5) + Li[BH3OtBu] + Li[BH(OtBu)3] + di-tert-butoxy-borane (22694-39-9)

Conditions	Yield
In tetrahydrofuran byproducts: THF; under N2, THF soln. of 1 equiv. of LiOBut in THF was added to 0.064 M soln. of BH3*THF in THF at -78 °C, warming to room temp.; the same result was obtained with mixing at room temp.; monitored by (11)B NMR; LiBH2(OBut)2 and LiB(OBut)4 were not formed;	A n/a B n/a C n/a D n/a E 0%

phthalatohydroborane-tetrahydrofurane adduct (950509-99-6) + hexane (110-54-3) + sodium t-butanolate (865-48-5) → Na{B(tert.-OC4H9)4} + Na{BH(tert.-OC4H9)3} + Na[BH(OtBu)3]-NaOB(OtBu)(OH)0.64H0.36*0.5C6H14 + tri-(tert-butyl)borate (7397-43-5) + di-tert-butoxy-borane (22694-39-9)

Conditions

Yield

In tetrahydrofuran byproducts: Na-phthalate; under N2, B-compd. in THF was added to THF soln. of Na-compd., solvent was removed, extd. with hexane and Et2O; using 3 equiv. of solid alkali-compd. gave reproducible result; monitored by (11)B NMR; hexane phase was crystd. for 2 weeks at -80 °C which lead to the solvated compd., Et2O contained NaB(OtBu)4, the hexane phase contained HB(OtBu)2 and B(OtBu)3;

Upstream product

• 11113-50-1 boric acid 
• 75-65-0 tert-butyl alcohol 
• 13292-87-0 dimethylsulfide borane complex 
• 4375-83-1 tris(dimethylamino)borane 
• 867-97-0 tris(diethylamino)borane 
• 1907-33-1 lithium tert-butoxide 
• 1240387-50-1 2-(dimethyl sulfide)-4,5-[1,2-dicarba-closo-dodecaborano⁽¹²⁾]-1,3-diselena-2-boracyclopentane 
• 950509-99-6 phthalatohydroborane-tetrahydrofurane adduct 
• 110-54-3 hexane 
• 865-48-5 sodium t-butanolate 
• 79812-14-9 Bis(diethylamino)(trimethylstannyl)boran 
• 150-46-9 triethyl borate 
• 121-43-7 Trimethyl borate 

Downstream Products

• 833-79-4 t-butyl 4-methoxybenzoate 
• 16537-09-0 t-butyl phenylacetate 
• 507-20-0 tertiary butyl chloride 
• 13460-50-9 metaboric acid 
• 593-90-8 trimethylborane 
• 38109-66-9 Dimethylborinsaeure-tert.-butylester 
• 819-38-5 CH₃B(O-t-C₄H₉)2 
• 11113-50-1 boric acid 
• 75-65-0 tert-butyl alcohol 
• 150-46-9 triethyl borate 
• 1351353-50-8 2-(5-(1,3-dioxolan-2-yl)thiophen-2-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane 
• 342636-66-2 (4-fluoro-3,5-dimethylphenyl)boronic acid 
• 139911-27-6 4-fluoro-3-methylphenyl boronic acid 
• 73774-45-5 di-(4-methoxyphenyl)borinic acid 

Relevant articles and documents

Synthesis, molecular structure and reactivity of the dimethyl sulfide adduct of a 1,3,2-diselenaborolane with an annelated dicarba-closo- dodecaborane(12) unit

The reaction of 1,2-diselenolato-1,2-dicarba-closo-dodecaborane(12) dianion [1,2-(1,2-C2B10H10)Se2] 2- with HBBr2-SMe2 affords the dimethylsulfide adduct of 4,5-[1,2-dicarba-closo-dodecaborano(12)]-1,3-diselena -2-borolane in good yield. The molecular structure was determined by X-ray diffraction, and the solution-state structure was established by NMR spectroscopy (1H, 11B, 13C, 77Se NMR). 11B and 77Se chemical shifts were reproduced by DFT calculations. Attempts were made to abstract dimethyl sulfide, and the parent donor-free compound could be detected in solution. The reactivity of the title compound was studied towards pyridine, Me3SnF,[Pt(PPh3)2(C2H 4)], tert-Bu -OH, AlMe3 and AlH3-N(Et)Me 2 as well as a hydroborating reagent.

Convergent synthesis of alpha -aryl- beta -ketonitriles

The present invention relates to processes for the production of alpha -aryl- beta -ketonitriles, which serve as synthetic intermediates in the preparation of a series of biologically important molecules such as corticotropin releasing factor (CRF) receptor antagonists.

Metall-Bor-Verbindungen, 13. Zur Synthese und Reaktivitaet einiger (Trimethylstannyl)borane

The preparation of some amino(trimethylstannyl)boranes and their chemical properties are described.With Me3SnLi (Me = CH3) as a reagent only the synthesis of Me3SnB(NR2)2 (1a, b), Me3SnBCl(NR2) (2a, b), and (Me3Sn)2BNR2 (3b) was achieved.The stannylboranes Me3SnB(NR2)2 show astonishing thermal stability.Their Sn - B bonds are broken by hydrogen, the halogens, and chalcogens as well as by alcohols.HCl cleaves the B - N bond.