Sodium borohydride

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Names

IUPAC name

Sodium tetrahydridoborate(1–)

Systematic IUPAC name

Sodium boranuide

Identifiers

CAS Number  16940-66-2 

 15681-89-7 (2D4) 

3D model  Interactive image

(JSmol)

ChEBI  CHEBI:50985 

ChemSpider  26189 

 9052313 (2D4) 

 9312193 (3T4) 

ECHA InfoCard 100.037.262 

EC Number  241-004-4

Gmelin 23167
Reference

MeSH Sodium+borohydride

PubChem CID  4311764

 23673181 (2D4)

 23671303 (3T4)

RTECS number  ED3325000

UNII  87L0B9CPPA 

UN number 1426

CompTox  DTXSID80893977 
Dashboard (EPA
)

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InChI

show

SMILES

Properties
Chemical NaBH4
formula

Molar mass 37.83 g/mol

Appearance white crystals

hygroscopic

Density 1.07 g/cm3[1]

Melting point 400 °C (752 °F; 673 K)(decomposes)[1]

Solubility in 550 g/L[1]

water

Solubility soluble in liquid ammonia, amines, pyridine

Structure[2]

Crystal structure Cubic (NaCl), cF8

Space group Fm3m, No. 225

Lattice constant a = 0.6157 nm

Hazards

GHS labelling:

Hazard H260, H301, H311, H314
statements

Precautionary P223, P231, P232, P280, P301+P310, P370+P378, P
statements
422

NFPA

704 (fire diamon

d)

3
1
2
W

Flash point 70 °C (158 °F; 343 K)

Autoignition ca. 220 °C (428 °F; 493 K)

temperature

Explosive limits 3%
 Lethal dose or concentration (LD, LC):

LD50 (median 160 mg/kg (Oral – Rat)

dose)
230 mg/kg (Dermal – Rabbit)

Related compounds

Other anions Sodium cyanoborohydride

Sodium hydride

Sodium borate

Borax

Sodium aluminum hydride

Other cations Lithium borohydride

Related Lithium aluminium hydride

compounds
Sodium triacetoxyborohydride

Except where otherwise noted, data are given for materials in

their standard state (at 25 °C [77 °F], 100 kPa).

 verify (what is   ?)

Infobox references

Sodium borohydride, also known as sodium tetrahydridoborate and sodium

tetrahydroborate,[3] is an inorganic compound with the formula NaBH4. This white solid,
usually encountered as a powder, is a reducing agent that finds application in chemistry,
both in the laboratory and on an industrial scale. It has been tested as pretreatment for
pulping of wood, but is too costly to be commercialized. [4][5] The compound is soluble
in alcohols, certain ethers, and water, although it slowly hydrolyzes.[6]
The compound was discovered in the 1940s by H. I. Schlesinger, who led a team
seeking volatile uranium compounds.[7][8] Results of this wartime research were
declassified and published in 1953.

Contents

 1Properties
o 1.1Structure
 2Synthesis and handling
 3Reactivity
o 3.1Organic synthesis
o 3.2Oxidation
o 3.3Coordination chemistry
o 3.4Protonolysis and hydrolysis
  4Applications
 5Safety
 6See also
 7References
 8External links

Properties[edit]
Solvent Solubility (g/100 mL)[6]

MeOH 13

EtOH 3.16

Diglym
5.15
e

Et2O insoluble

Sodium borohydride is an odorless white to gray-white microcrystalline powder that

often forms lumps. It can be purified by recrystallization from warm (50 °C) diglyme.
[9]
 Sodium borohydride is soluble in protic solvents such as water and lower alcohols. It
also reacts with these protic solvents to produce H2; however, these reactions are fairly
slow. Complete decomposition of a methanol solution requires nearly 90 min at 20 °C.
[10]
 It decomposes in neutral or acidic aqueous solutions, but is stable at pH 14. [6]
Structure[edit]
NaBH4 is a salt, consisting of the tetrahedral [BH4]− anion. The solid is known to exist as
three polymorphs: α, β and γ. The stable phase at room temperature and pressure is α-
NaBH4, which is cubic and adopts an NaCl-type structure, in the Fm3m space group. At
a pressure of 6.3 GPa, the structure changes to the tetragonal β-NaBH4 (space
group P421c) and at 8.9 GPa, the orthorhombic γ-NaBH4 (space group Pnma) becomes
the most stable.[11][12][13]

α-NaBH4 β-NaBH4 γ-NaBH4

Synthesis and handling[edit]

For commercial NaBH4 production, the Brown-Schlesinger process and the Bayer
process are the most popular methods. In the Brown-Schlesinger process sodium
borohydride is industrially prepared from sodium hydride (produced by reacting Na and
H2) and trimethyl borate at 250–270 °C:
B(OCH3)3 + 4 NaH → NaBH4 + 3 NaOCH3
Millions of kilograms are produced annually, far exceeding
the production levels of any other hydride reducing agent.
[4]
 It can also be produced from inorganic borates,
including borosilicate glass[14] and borax (Na2B4O7):
Na2B4O7 + 16 Na + 8 H2 + 7 SiO2 → 4 NaBH4 + 7 Na2SiO3
Magnesium is a less expensive reductant, and could in
principle be used instead:[15][16]
8 MgH2 + Na2B4O7 + Na2CO3 → 4 NaBH4 + 8 MgO + CO2
and
2 MgH2 + NaBO2 → NaBH4 + 2 MgO

Reactivity[edit]
Organic synthesis[edit]
NaBH4 reduces many organic carbonyls,
depending on the precise conditions. Most
typically, it is used in the laboratory for
converting ketones and aldehydes to alcohols. It
efficiently reduces acyl chlorides, anhydrides, α-
hydroxylactones, thioesters, and imines at room
temperature or below. It reduces esters slowly
and inefficiently with excess reagent and/or
elevated temperatures, while carboxylic acids
and amides are not reduced at all.
[17]
 NaBH4 reacts with water and alcohols, with
evolution of hydrogen gas and formation of the
corresponding borate, the reaction being
especially fast at low pH.
Nevertheless, an alcohol, often methanol or
ethanol, is generally the solvent of choice for
sodium borohydride reductions of ketones and
aldehydes. The mechanism of ketone and
aldehyde reduction has been scrutinized by
kinetic studies, and contrary to popular
depictions in textbooks, the mechanism does not
involve a 4-membered transition state like
alkene hydroboration,[18] or a six-membered
transition state involving a molecule of the
alcohol solvent.[19] Hydrogen-bonding activation is
required, as no reduction occurs in an aprotic
solvent like diglyme. However, the rate order in
alcohol is 1.5, while carbonyl compound and
borohydride are both first order, suggesting a
mechanism more complex than one involving a
six-membered transition state that includes only
a single alcohol molecule. It was suggested that
the simultaneous activation of the carbonyl
compound and borohydride occurs, via
interaction with the alcohol and alkoxide ion,
respectively, and that the reaction proceeds
through an open transition state.[20][21]
α,β-Unsaturated ketones tend to be reduced by
NaBH4 in a 1,4-sense, although mixtures are
often formed. Addition of cerium chloride
improves the selectivity for 1,2-reduction of
unsaturated ketones (Luche reduction). α,β-
Unsaturated esters also undergo 1,4-reduction
in the presence of NaBH4.[6]

The NaBH4-MeOH system, formed by the

addition of methanol to sodium borohydride in
refluxing THF, reduces esters to the
corresponding alcohols.[22] Mixing water or an
alcohol with the borohydride converts some of it
into unstable hydride ester, which is more
efficient at reduction, but the reductant
eventually decomposes spontaneously to
produce hydrogen gas and borates. The same
reaction can also occur intramolecularly: an α-
ketoester converts into a diol, since the alcohol
produced attacks the borohydride to produce an
ester of the borohydride, which then reduces the
neighboring ester.[23]
The reactivity of NaBH4 can be enhanced or
augmented by a variety of compounds.[24][25]
Oxidation[edit]
Oxidation
with iodine in tetrahydrofuran gives borane–
tetrahydrofuran, which can reduce carboxylic
acids.[26]
Partial oxidation of borohydride with iodine
gives octahydrotriborate:[27]
3 BH4− + I2 → B3H8− + 2 H2 + 2 I−
Coordination chemistry[edit]
BH4− is a ligand for metal ions. Such
borohydride complexes are often prepared
by the action of NaBH4 (or the LiBH4) on the
corresponding metal halide. One example is
the titanocene derivative:[28]
2 (C5H5)2TiCl2 + 4 NaBH4 → 2 (C5H5)2TiBH4 + 4 NaCl +
B2H6 + H2
Protonolysis and hydrolysis[edit]
In the presence of metal catalysts,
sodium borohydride hydrolyzes with
release of hydrogen. Exploiting this
reactivity, sodium borohydride has been
used in prototypes of the direct
borohydride fuel cell.
NaBH4 + 2 H2O → NaBO2 + 4 H2 (ΔH < 0)

Applications[edit]
The principal application of sodium
borohydride is the production
of sodium dithionite from sulfur
dioxide: Sodium dithionite is used as
a bleaching agent for wood pulp and
in the dyeing industry.
Sodium
borohydride reduces aldehydes and k
etones to give the related alcohols.
This reaction is used in the
production of various antibiotics
including chloramphenicol, dihydrostr
eptomycin, and thiophenicol. Various
steroids and vitamin A are prepared
using sodium borohydride in at least
one step.[4]
Sodium borohydride has been
considered as a solid state hydrogen
storage candidate. Although practical
temperatures and pressures for
hydrogen storage have not been
achieved, in 2012 a core–
shell nanostructure of sodium
borohydride was used successfully to
store, release and reabsorb hydrogen
under moderate conditions.[29]
Sodium borohydride can be used to
reduce foxing in old books and
documents.[30] This treatment should
only be done by a skilled professional
conservator/restorer as damage to
paper can ensue if the reducing agent
is not applied correctly, such as over
bleaching and bubbling of paper.

Safety[edit]
Sodium borohydride is a source
of hydrogen or diborane, which are
both flammable. Spontaneous ignition
can result from solution of sodium
borohydride in dimethylformamide.
Bulk solutions of sodium borohydride
are often prepared with excess
sodium hydroxide, which is corrosive.

See also[edit]
Many derivatives and analogues of
sodium borohydride exhibit modified
reactivity of value in organic
synthesis.[31]

 Sodium
triacetoxyborohydride, a
milder reductant owing to
the presence of more
electron-withdrawing
acetate in place of hydride.
 Sodium triethylborohydride,
a stronger reductant owing
to the presence of electron-
donating ethyl groups in
place of hydride.
 sodium cyanoborohydride,
a milder reductant owing to
the presence of more
electron-withdrawing
cyanide in place of hydride.
 Useful for reductive
aminations.

 Lithium borohydride, a
more strongly reducing
reagent.
 L-selectride (lithium tri-sec-
butylborohydride), a more
strongly reducing are
derivative.

 Lithium aluminium hydride,

a more strongly reducing
reagent, capable of
reducing esters and
amides.

References[edit]
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M., ed. (2011).  CRC

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54002034.
3. ^ Busch, D.H.
(2009).  Inorganic
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Their Mixtures".  Industrial &
Engineering Chemistry
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 2005.  doi:10.1063/1.2158505
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12. ^ Filinchuk, Y.; Talyzin, A. V.;
Chernyshov, D.; Dmitriev, V.
(2007).  "High-pressure phase
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Hao; Li, Hai-Wen; Zhu, Min
(2018).  "A Recycling
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48.
21. ^ Wigfield, Donald C.
(January 1979).
"Stereochemistry and
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reductions by hydride
reagents".  Tetrahedron. 35 (
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462.  doi:10.1016/0040-
4020(79)80140-4. ISSN 0040
-4020.
22. ^ da Costa, Jorge C.S.; Pais,
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Mendonça, Jorge S.; de
Souza, Marcus V. N.; Peralta,
Mônica A.; Vasconcelos,
Thatyana R.A.
(2006).  "Simple reduction of
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 133. Retrieved  29
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23. ^ Dalla, V.; Catteau, J.P.;
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External links[edit]
 National Pollutant
Inventory – Boron and
compounds
 MSDS for Sodium
Borohydride
 Materials & Energy
Research Institute Tokyo,
Ltd.
 Chemo- and
stereoselectivity using
Borohydride reagents
 Material Safety Data Sheet
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Sodium compounds

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 Borohydrides
 Reducing agents
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Trimethylsilyl chloride
From Wikipedia, the free encyclopedia
Jump to navigationJump to search

Trimethylsilyl chloride
 Names

Preferred IUPAC name

Chlorotri(methyl)silane

Other names

Trimethylsilyl chloride

Chlorotrimethylsilane

TMSCl

Trimethylchlorosilane

TMCS

Identifiers

CA  75-77-4 
S
Nu
mbe
r

3D  Interactive image
mod
el
(JS
mol)
Che  6157 

mSp

ider

EC 100.000.819 

HA

Info

Car

EC  200-900-5

Nu

mbe

Pub  6397
Che
m C
ID

RTE  VV2710000

CS

num

ber

UNI  62UO4690X6 

UN 1298

num

ber

Co  DTXSID2024822 
mpT
ox
Das
hbo
ard (
EPA
)

show

InChI
 show

SMILES

Properties

Che C3H9SiCl
mic
al
for
mul
a

Mol 108.64 g/mol

ar

mas

App Colorless liquid, fumes in moist air

eara

nce

Den 0.856 g/cm3, liquid

sity

Melt −40 °C (−40 °F; 233 K)

ing

poin

Boil 57 °C (135 °F; 330 K)

ing

poin

Solu Reacts
bilit
y in
wate
r

Mag −77.36·10−6 cm3/mol
neti
c
susc
epti
bilit
y (χ)

Structure

Mol Tetrahedral at Si
ecul
ar
shap
e

Hazards

GHS labelling:

Pi
ct
o
gr
a
m
s

Si Danger
g
n
al
w
or
d

H H225, H301, H312, H314, H331, H351
a
z
ar
d
st
at
e
m
e
nt
s

P P201, P202, P210, P233, P240, P241, P242, P243, P260, P261, P
re
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Related compounds

Rela Trimethylsilyl fluoride

ted 
Trimethylsilyl bromide
halo
silan Trimethylsilyl iodide
es

Except where otherwise noted, data are given for materials in

their standard state (at 25 °C [77 °F], 100 kPa).

 verify (what is   ?)

 Infobox references
"TMCS" redirects here. For the history of Ticketmaster Online–CitySearch (TMCS),
see IAC (company) §  1980s and 1990s. For the Turtle Mountain Community School in
North Dakota, see Belcourt School District.
Trimethylsilyl chloride, also known as chlorotrimethylsilane is an organosilicon
compound (silyl halide), with the formula (CH3)3SiCl, often
abbreviated Me3SiCl or TMSCl. It is a colourless volatile liquid that is stable in the
absence of water. It is widely used in organic chemistry.

Contents

 1Preparation
 2Reactions and uses
o 2.1Silylation in organic synthesis
o 2.2Other reactions
 3References

Preparation[edit]
TMSCl is prepared on a large scale by the direct process, the reaction of methyl
chloride with a silicon-copper alloy. The principal target of this process
is dimethyldichlorosilane, but substantial amounts of the trimethyl and monomethyl
products are also obtained.[1] The relevant reactions are (Me = CH3):
x MeCl + Si → Me3SiCl, Me2SiCl2, MeSiCl3, other
products
Typically about 2–4% of the product stream is the
monochloride, which forms an azeotrope with MeSiCl 3.

Reactions and uses[edit]

TMSCl is reactive toward nucleophiles, resulting in the
replacement of the chloride. In a characteristic reaction of
TMSCl, the nucleophile is water, resulting in hydrolysis to
give the hexamethyldisiloxane:
2 Me3SiCl + H2O → Me3Si-O-SiMe3 + 2 HCl
The related reaction of trimethylsilyl chloride with
alcohols can be exploited to
produce anhydrous solutions of hydrochloric acid in
alcohols, which find use in the mild synthesis
of esters from carboxylic acids and nitriles as well
as, acetals from ketones. Similarly, trimethylsilyl
chloride is also used to silanize laboratory glassware,
making the surfaces more lipophilic.[2]
Silylation in organic synthesis[edit]
By the process of silylation, polar functional groups
such as alcohols and amines readily undergo reaction
with trimethylsilyl chloride, giving trimethylsilyl
ethers and trimethylsilyl amines. These new
groups "protect" the original functional group by
removing the labile protons and decreasing the basicity
of the heteroatom. The lability of the Me3Si-O and
Me3Si-N groups can later be removed
("deprotected"). Trimethylsilylation can also be used to
increase the volatility of a compound, enabling gas
chromatography of normally nonvolatile substances
such as glucose. Trimethylsilyl chloride also reacts with
metal acetylides to give trimethylsilyl alkynes such
as bis(trimethylsilyl)acetylene. Such derivatives are
useful protected forms of alkynes.
In the presence of triethylamine and lithium
diisopropylamide, enolisable aldehydes, ketones and es
ters are converted to trimethylsilyl enol ethers.[3] Despite
their hydrolytic instability, these compounds have found
wide application in organic chemistry; oxidation of
the double bond by epoxidation or dihydroxylation can
be used to return the original carbonyl group with
an alcohol group at the alpha carbon.
The trimethylsilyl enol ethers can also be used as
masked enolate equivalents in the Mukaiyama aldol
addition.
Other reactions[edit]
Trimethylsilyl chloride is used to prepare other
trimethylsilyl halides and pseudohalides, including
trimethylsilyl fluoride, trimethylsilyl
bromide, trimethylsilyl iodide, trimethylsilyl
cyanide, trimethylsilyl azide,[4] and trimethylsilyl
trifluoromethanesulfonate (TMSOTf). These compounds
are produced by a salt metathesis reaction between
trimethylsilyl chloride and a salt of the (pseudo)halide
(MX):
MX + Me3Si-Cl → MCl + Me3Si-X
TMSCl, lithium, and nitrogen molecule react to
give tris(trimethylsilyl)amine, under catalysis
by nichrome wire or chromium trichloride:
3 Me3SiCl + 3 Li + 1⁄2 N
2 → (Me3Si)3N + 3 LiCl
 Using this approach, atmospheric nitrogen can
be introduced into organic substrate. For
example, tris(trimethylsilyl)amine reacts with
α,δ,ω-triketones to give tricyclic pyrroles.[5]
Reduction of trimethylsilyl chloride
give hexamethyldisilane:
2 Me3SiCl + 2 Na → 2 NaCl + Me3Si-SiMe3

References[edit]
1. ^ Röshe, L.; John, P.; Reitmeier, R.
"Organic Silicon
Compounds". Ullmann's Encyclopedia
of Industrial Chemistry. Weinheim:
Wiley-VCH.  do
i:10.1002/14356007.a24_021.
2. ^ Such as in Norbert Zander and
Ronald Frank (2005).  "The use of
polystyrylsulfonyl chloride resin as a
solid supported condensation reagent
for the formation of esters: Synthesis
of N-[(9-fluorenylmethoxy)carbonyl]-L-
aspartic acid; α tert-butyl ester, β-(2-
ethyl[(1E)-(4-
nitrophenyl)azo]phenyl]amino]ethyl
ester". Organic Syntheses.  81: 235.
3. ^ Yoshihiko Ito, Shotaro Fujii, Masashi
Nakatuska, Fumio Kawamoto, and
Takeo Saegusa (1979).  "One-Carbon
Ring Expansion of Cycloalkanones to
Conjugated Cycloalkenone: 2-
Cyclohepten-1-one".  Organic
Syntheses.  59: 113.; Collective
Volume, 1, p.  327
4. ^ L. Birkofer and P. Wegner
(1970).  "Trimethylsilyl azide".  Organic
Syntheses.  50: 107.; Collective
Volume, 6, p.  1030
5. ^ Brook, Michael A. (2000).  Silicon in
Organic, Organometallic, and Polymer
Chemistry. New York: John Wiley &
Sons. pp. 193–194.

Categories: 
 Reagents for organic chemistry
 Trimethylsilyl compounds
 Chlorine compounds
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