Article No : a04_447
Butanals
BOY CORNILS, formerly Hoechst AG, Frankfurt/M., Federal Republic of Germany
RICHARD W. FISCHER, Celanese Chemicals Europe GmbH, Werk Ruhrchemie,
Oberhausen, Federal Republic of Germany
CHRISTIAN KOHLPAINTNER, Celanese Chemicals Europe GmbH, Werk Ruhrchemie,
Oberhausen, Federal Republic of Germany
1. Introduction. . . . . . . . . . . . . . . . . . . .
2. Physical Properties . . . . . . . . . . . . . .
3. Production . . . . . . . . . . . . . . . . . . . . .
4. Stabilization, Testing, and Quality
Specifications . . . . . . . . . . . . . . . . . . .
5. Handling, Storage, and Shipment . . .
1. Introduction
Butanals are saturated aliphatic C4 aldehydes,
C4H8O, Mr 72.11. There are two isomers:the
straight-chain butyraldehyde [123-72-8] (buta-
nal) and the branched isobutyraldehyde [78-84-
2] (2-methylpropanal, dimethylacetaldehyde).
Butyraldehyde Isobutyraldehyde
Both aldehydes are found in minor concentra-
tions in various essential oils, in plants, as well
as in other natural substances [1], [2]. Both
butyraldehyde and isobutyraldehyde are highly
reactive intermediates that serve as versatile
building blocks for many chemical syntheses,
predominantly for the preparation of C4 – C8
compounds.
The annual production volume of butyralde-
hydes is several million tones worldwide. The
total production capacity for n-butanal is
6.8
106 t with a demand of 5.9
106 t. The
annual growth rate is estimated to be 2 – 4 %.
Production on an industrial scale is performed
exclusively by hydroformylation (! Oxo Syn-
thesis) [3–5]. World-scale plants such as those
operated by BASF, Oxeno (Degussa-H€ uls), Ce-

2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
DOI: 10.1002/14356007.a04_447
. . . . . . 397 6. Chemical Reactions and Applications . . . . . . 401
. . . . . . 397 7. Toxicology . . . . . . . . . . . . . . . . . . . . . . . . . . . 404
. . . . . . 397 References . . . . . . . . . . . . . . . . . . . . . . . . . . . 404
. . . . . . 400
. . . . . . 401
lanese, and UCC have an annual output of
(200 – 600)
103t.
2. Physical Properties
n-Butyraldehyde and isobutyraldehyde are col-
orless, flammable liquids with a pungent pene-
trating odor. Their vapors have a narcotic effect
and irritate the mucous membranes. Both iso-
mers are miscible with organic solvents, such as
alcohols, ethers, and benzene. The solubilities of
the butyraldehydes in water are collected in
Table 1. Some physical data of the butyralde-
hydes are compiled in Table 2. Table 3 gives the
composition of some binary and ternary azeo-
tropes. Further physical properties are provided
in [1], [2], and [6].
3. Production
The only process used for manufacturing butyr-
aldehydes is the hydroformylation (! Oxo Syn-
thesis) of propylene. The initially formed alde-
hyde can be hydrogenated to the corresponding
alcohol, oxidized to the acid, or converted to
other derivatives. Other routes, such as the hy-
drogenation of crotonaldehyde, prepared by the
dimerization of acetaldehyde, and the dehydro-
genation of butanols, are obsolete and not used on
an industrial scale.
398 Butanals Vol. 6

Table 1. Solubility of butyraldehydes in water and of water in butyraldehydes (mass fractions in %)

Aldehyde in water Water in aldehyde

Temperature,  C Butyraldehyde Isobutyraldehyde Butyraldehyde Isobutyraldehyde

0 9.8 9.3 3.2 2.1

10 8.6 7.8 2.8 2.0
20 7.6 6.7 2.6 1.9
30 6.8 5.8 2.4 1.9
40 6.1 5.0 2.4 2.0
50 2.4 2.1

Table 2. Physical properties of butyraldehydes hydroformylation is carried out at 90 – 180  C

and 2.0 – 30 MPa [3–5].
Butyraldehyde Isobutyraldehyde
Basically, all olefins, diolefins, or even func-
Melting point,  C  97  66 tionally substituted olefins may be used as raw
Boiling point,  C 74.8 64
Density at 20  C, g/cm3 0.803 0.788
materials. On an industrial scale alkenes from C2
Refractive index n20D 1.3805 1.3730 to C18 are predominantly used. Propylene has
Viscosity at 20  C, mPa s 0.45 0.45 gained particular significance, being converted to
Specific heat capacity a mixture of n- and isobutyraldehyde. Although
at 25 – 30  C, J g1 K1 2.123 2.544
Heat of vaporization
the reaction medium is homogeneous in most
at the boiling point, J/g 436 409 processes, a two-phase process (water/organic
Heat of combustion, kJ/mol  2478.7  2510 solvent) has also been developed, with advanta-
Crit. pressure, mPa 4.06 ca. 4.3 geous catalyst separation and optimized energy
Crit. density, g/cm3 0.259
Crit. temperature,  C 248 ca. 267
consumption.
Surface tension at 20  C, mN/m 24.6 24
Dielectric constant at 20  C 14.9 13.5
Vapor pressure at 20  C, kPa 12 17
Dipole moment (vapor), Debye 2.72
Coefficient of expansion
at 20 – 30  C, K1 0.0013 0.0014

On industrial scale depending on the oxo

Hydroformylation of Propylene. In the
hydroformylation process discovered by OTTO
ROELEN at Ruhrchemie in 1938, a Cn olefin is
treated with synthesis gas in the presence of a
catalyst to form a Cnþ1 aldehyde. Transition-
metal hydridocarbonyl complexes of the general
formula [HM (CO)x](M ¼ Co, Rh, Ru) serve as a
homogeneous catalysts. On an industrial scale,
Table 3. Azeotropic mixtures with butyraldehydes
catalyst, the reaction conditions, and the
process design, the mixture of n/iso
butyraldehyde with a ratio of almost 95:5 is
obtained respectively. In addition to the
aldehydes, which constitute 90 – 98 % of the
reaction mixture, minor amounts of byproducts
and secondary pro-ducts of the reactive
butyraldehydes are formed, such as butyl
formate, butanols, and aldehyde dimers,
trimers, and condensation products [3–5].

Concentration
Boiling point of B (C) in the
Compound A Compound B Compound C of azeotrope,  C azeotrope, wt %

Butyraldehyde ethanol 70.7 60.6

Butyraldehyde water 68 8.8
Butyraldehyde hexane 60 74
Butyraldehyde ethanol water 67.2 11 (9)
Isobutyraldehyde water 60.5 6.0
Vol. 6
Oxo Technology [7]. The oxo reaction (hy-
droformylation) is the reaction of synthesis gas
(CO/H2, usually with a 1/1 molar ratio) with an
alkene (see also ! Oxo Synthesis). Terminal
olefins yield a mixture of n-aldehydes and 2-
methylaldehyde isomers, the so-called isoalde-
hydes. The reaction is catalyzed by rhodium or
cobalt metal complexes. With unmodified hydri-
do rhodium or cobalt species the n/iso ratio is
usually poor. By addition of ligands like triphe-
nylphosphine (TPP) in homogeneous systems or
trisulfonated triphenyl phosphine (TPPTS) in
water/organic two-phase systems the n/iso ratio
is significantly enhanced. In particular at low
temperatures, at high carbon monoxide partial
pressure, and at a high ligand concentrations the
formation of the straight-chain isomers is favored
[3–5].
Early versions of the oxo process used cobalt
catalysts at relatively high pressures (20 –
35 MPa), whereby [HCo (CO)4] is the active
catalyst species. The typical n/iso ratio is about
4/1 with propylene as feedstock. By the mid-
1900s various companies (e.g., BASF, ICI, East-
man) had developed their own versions of the
cobalt process. For short-chain olefins like pro-
pylene, the cobalt technology has almost fully
been substituted by rhodium-based processes.
Only for higher and in particular branched olefins
is cobalt still the most widely applied metal. The
second-generation, phosphine-modified cobalt
hydroformylation catalysts were developed in
the 1960s by Shell.
In the 1970s UCC and Celanese developed a
low-pressure oxo process (LPO)with Rh as metal
and triphenylphosphine (TPP) as ligand. This
process operates at a lower pressure and yields
a n/iso ratio of about 10/1. Versions of this
process with a gas recycle step are commonly
known as LP Oxo Mk I (early version) or Mk II.
A further proposal is the LPO Mk III process
with improved raw material usage and a liquid
catalyst recycle. The product/catalyst separation
is performed in a separate vessel in which the
aldehyde vapors are flashed off and the liquid
solution containing the rhodium catalyst is re-
cycled to the reactor. In this operating mode, the
aldehyde condensation products serve as a sol-
vent for the catalyst. However, the application of
all versions is mostly limited to propylene and
butene hydroformylation. Many plants have been
converted from high-pressure cobalt to LPO
Butanals 399
technology for new or additional butyraldehyde
(and thus butanol and 2-ethylhexanol) capacity.
By the mid-1980s Ruhrchemie (now Cela-
nese) and Rhône-Poulenc developed a two-phase
process with a water-soluble rhodium/TPPTS
complex. The major advantages are the simple
and mild catalyst recycle, the high n/iso ratio of
ca. 20/1 and the beneficial low energy consump-
tion of the whole process [3–5], [8].
The fourth generation of oxo catalysts used for
the production of butyraldehyde and especially
of higher aldehydes (and thus less important for
synthesis of butyraldehyd) is known as the LPO
Mk IV version. This process applies highly active
bis-phosphite-modified rhodium catalysts which
are suitable for both propylene and raffinate II
feedstocks for butyraldehyde and valeraldehyde,
respectively. The high catalyst activity allows
this process to be run in single-pass mode with no
olefin-recycle requirements. The potential of this
process is its flexibility to convert propylene or
butenes in the same reactor system.
Process Technology. For homogeneous re-
action systems, the standard processing of the
crude hydroformylation product, containing n-
and isobutyraldehyde, rhodium metal, ligand,
and byproducts, is generally the distillation of
the reaction mixture to separate the aldehydes
from the catalyst solution. To minimize catalyst
decomposition, phosphine-modified cobalt or
rhodium catalysts are separated from the reaction
product by fast flash distillation. The less volatile
catalysts remain at the bottom and are recycled to
the hydroformylation reactor without further
treatment. However, optimized catalyst lifetime
and thus improved activity and selectivity re-
quires the discharge of a small portion of the
catalyst for workup and addition of fresh catalyst.
In contrast to the homogeneous hydroformy-
lation processes, the Ruhrchemie/Rhône-Pou-
lenc process (RCH/RP) is designed on a
completely different reaction and catalyst recov-
ery system. In principle the two-phase RCH/RP
process applies a stirred tank reactor, followed by
a phase separator and a stripping column. The
reactor containing the aqueous catalyst solution
(Rh/TPPTS) is fed with propylene and synthesis
gas. The crude oxo product is passed on to the
phase separator, where gaseous components are
removed and the liquids separated into two
phases, the aqueous catalyst solution and the
400 Butanals Vol. 6
organic aldehyde phase. The catalyst solution is CH3 CH2 CH2 CH2 OH
CH3 CH2 CH2 CHOþH2
recycled to the reactor via a heat exchanger
system, which generates steam. Propylene
conversion by this process is 90-96%. This The reaction is carried out in the gas phase
results in one of the advantages of the two- with a heterogeneous catalyst [19]. The addition
phase technol-ogy:the high energy efficiency. of hydrogen acceptors such as O2, either pure or
as air, increases the aldehyde yield but also the
The Rh/P ratio is kept to 0.001:1 to ensure an n/
iso ratio of at least 95/5. Vapours of N and I formation of byproducts. Zinc- and/or chromi-
Butanal are formed from 1-2% of mixture at um-doped copper catalysts are particularly effec-
390-460K in an adiabatic CSTR reactor. tive [20], [21].
The organic phase containing the crude
aldehydes is stripped with synthesis gas to Fischer – Tropsch Synthesis generates
remove dissolved propylene upto 98%, which small amounts of n-butyraldhyde, which is of
is recycled to the reactor. The raw aldehyde importance in some local markets [16], [22].
mix-ture is split into iso- and n-
butyraldehydes in a distillation unit.

Hydrogenation of Crotonaldehyde. Be-fore 4. Stabilization, Testing, and Quality

the discovery of the hydroformylation reac-tion,
the aldol condensation of acetaldehyde to give
Specifications
crotonaldehyde followed by hydrogenation to n-
Stabilization. The reactivity of butanals is
butyraldehyde was the most important meth-od
determined by the polarity of the carbonyl group.
of producing n-butyraldehyde.
The inductive effect of the carbonyl group pro-
motes a-proton abstraction, which allows a
broad variety of consecutive intermolecular re-
actions, with addition type reactions as the most
important examples. Thus it is recommended to
handle aldehydes during distillative work-up,
n-Butanol is formed as a byproduct by hydro- storage and shipment only under the following
genation of the aldehyde moiety during the se- precautions:
lective hydrogenation of the double bond of
crotonaldehyde. Selective hydrogenation is per- . Inert gas atmosphere for all reaction and work-
formed in gas- or liquid-phase processes. Typical up steps
catalysts applied are supported catalysts on the . Storage with exclusion of UV light
basis of Cu, Ni, Pd, Ru, Fe, Cr, or Mn [1], [9–14]. . Storage at constant and moderate temperature
Up to the 1950s this route was still the pre- . Conversion into thermally stable compounds
ferred method for producing n-butyraldehyde like acetals, which are easily cleaved back to
[15] on an industrial scale, but the convenient the aldehydes
one-stage oxo processes replaced crotonalde- . Addition of stabilizers and antioxidants
hyde hydrogenation almost completely. Only
countries with massive ethanol production based Testing. The most important method of test-
on natural resources, such as Brazil, might redis- ing and continuous control of product quality
cover the crotonaldehyde route for producing n- (Table 4) is gas chromatography with a low
butyraldehyde [15]. injection temperature to avoid decomposition of
impurities, e.g., aldols.
Dehydrogenation of Butanols. Butanols In the analysis of butyraldehydes it is impor-
formed in other processes, such as Fischer – tant to detect trimeric aldehydes, which are
Tropsch synthesis [16], alcoholic fermentation formed readily, especially in the absence of
of sugar with Clostridium saccharobutylaceto- stabilizers. Since these trimerization reactions
nium liquefaciensor Bacillus amylobacter [17], are catalyzed by acids, contact with acidic com-
and Reppe carbonylation [18], can be dehydro- pounds must be strictly avoided during the course
genated to butyraldehydes. of aldehyde processing. During the analysis of
Vol. 6 Butanals 401

Table 4. Delivery specifications for butyraldehydes [23]

Butyraldehyde Isobutyraldehyde

Method moist dry moist dry

Butyraldehyde, wt % GLC 3 96.0 3 99.0 2 0.5 2 0.2

Isobutyraldehyde, wt % GLC 2 0.3 3 95.0 3 99
Density at 20  C, kg/L DIN 51757, ASTM D 1298 0.807 – 0.812 0.801 – 0.803 0.790 – 0.794 0.786 – 0.790
Refractive index n20D DIN 51423, ASTM D 1747 1.380 – 1.382 1.373 – 1.376 1.372 – 1.374
Color, Pt-Co scale DIN 53409, ASTM D 1209 2 15 2 10 2 15 2 15
Acid number, mg KOH/g DIN 53402, ASTM D 1613 2 3.0 22 2 3.0 2 2.0
Water, wt % Karl Fischer 2 3.0 2 0.2 2 2.0 2 0.1
Distillation range (95 vol%) ASTM D 1078 67 – 80 ca. 74 – 76 57 – 70 63 – 67
at 101.3 kPa,  C (~t 2 2  C)

water in butyraldehyde by Karl Fischer titration,
special precautions must be taken to avoid con-
densation to acetals, which is accompanied by
formation of water. This is achieved by the use of
a solvent mixture composed of four parts pyri-
dine and one part ethylene glycol. The density
and refractive index of the water-containing
product are strongly affected by the equilibrium
hydrate concentration, which is established slow-
ly. During determination of the acid number care
must be taken to exclude atmospheric oxygen.
The boiling point of the butyraldehydes is strong-
ly affected by traces of water.
Quality Specifications. Table 4 outlines
the standard quality specifications for butyral-
dehydes. The limits are largely determined by
the intended use and by specific customer
requests.
Owing to the low flash points and ignition
temperatures (Table 5) as well as the high vola-
tility of these aldehydes the safety regulations are
to be strictly observed.
The butyraldehydes are shipped in tank cars or
trucks, tankers, or drums. The classification and
designations for the various modes of transport
must be observed (Table 5).
6. Chemical Reactions and
Applications
Owing to their reactivity butyraldehydes are
important starting materials for a broad variety
of products [30]. Due to the high reactivity of the
carbonyl group, aldehydes undergo many organ-
ic chemical reactions. Typical aldehyde reac-
tions are:

. Addition to the C¼O bond without substitution

5. Handling, Storage, and Shipment
The butyraldehydes are stored and shipped in
containers of corrosion-resistant steel, alumi-
num, glass, or ceramic, as well as specially
coated tanks of normal steel and drums with
removable polyethylene inserts. Even with water
contents below 0.1 % and storage under inert gas,
n-butyraldehyde dissolves iron from steel, caus-
ing discoloration of the product.
On contact with air butyraldehyde is oxidized
readily to the butyric acids. Therefore, storage
under inert gas is mandatory. Even traces of acids
catalyze the trimerization of isobutyraldehyde. In
general this may be prevented by the addition of a
suitable amine (e.g., triethanolamine) or other
bases [24].
of the oxygen atom
. Addition to the C¼O bond under substitution
of the generated hydroxyl group
. Substitution of the oxygen functionality
. Formation of enol derivatives
. Oxidation
. Reduction
. C–C bond cleavage
. C–C bond formation.
Figure 1 outlines the reactions applied on
industrial scale.
Butyraldehydes are important intermediate
products for a vast number of C4 products, in-
cluding n-butanol, n-butyric acid, n-butylamines,
and butyl acrylates, as well as for the plasticizer
alcohol 2-ethylhexanol (C8) and for C6 products
402 Butanals Vol. 6

Table 5. Safety information for butyraldehydes*

Butyraldehyde Isobutyraldehyde

Flash point, closed cup (DIN 51755) C  13 <  18
Lower and upper explosive
limit in air at 101.3 kPa vol% 1.94 – 12.5 1.6 – 11
Autoignition temperature

(DIN 51794, ASTM D 2155) C 190 165
Odor threshold low low
LD50 (oral, rat) g/kg 2.5 – 5.9 2.8 – 3.7
LD50 (dermal, rabbit) g/kg 3.56 3.7 – 7.1
LCLo (inhal., rat) mg/15 min 23.9 23.2
LDLo (subcut., rat) g/kg 10
Marking according to Regulations
of the European Community Symbol F F*
R-Phrases 11 11*
S-Phrases (2)-9-29-33 9-16-29-33-36*
Hazard classification for transport:
RID/ADR 3b 3b
(Class, Item Number)
IMDG-Code
(Class, UN No., Packing Gp.) 3.2, 1129, II 3.1, 2045, II
IATA-DGR (ICAO Techn. Instr.)
(Class, UN No., Packing Gp.) 3, 1129, II 3, 2045, II
Mail (FRG) max. 125 cm3 per receptacle and
max. 500 cm3 per consignment
DOT (USA) flammable liquid
*
Vapor pressure at 20  C, solubility of butyraldehydes in water and vice versa: see Tables 1 and 2
**
No EEC regulation; marking corresponds to n-butyraldehyde.

such as 2-ethylbutyric acid. Isobutyraldehyde is
converted mainly to isobutanol and neopentyl
glycol. Isobutyric acid is a potential intermediate
for methacrylic acid (! Methacrylic Acid and
Derivatives, Section 3.3.).
Hydrogenation. The butyraldehydes are
converted to the corresponding butanols by cata-
lytic hydrogenation, whereby both liquid-phase
and gas-phase processes are used. The mild,
highly selective gas-phase hydrogenation is car-
ried out on nickel or copper supported catalysts.
Oxidation. Pure oxygen or air converts bu-
tyraldehydes to carboxylic acids in high yields,
the reaction taking place in the presence or even
absence of a catalyst. Transition metals of
Groups 5 – 10, Cu, Ag, Ce, the alkali metals,
and alkaline earth metals are suitable catalysts. If
oxidation is carried out in the liquid phase, the
metal naphthenates or carboxylates are used. In
gas-phase processes, generally metal oxides, de-
posited on carriers such as silica gel, kieselguhr,
silicates, quartz, or alumina, are used [1]. For
further information, see [1], [31–33], [34].
The use of specific metal oxide catalysts
allows isobutyraldehyde to be oxidized at high
temperature directly to methacrolein, or
methacrylic acid, or a mixture of the two [1],
[35–38]. By variation of the reaction conditions,
acetone or isopropyl alcohol is accessible [1],
[39]. n-Butyric anhydride is also produced by
oxidation of n-butyraldehyde [1].
Addition and Condensation Reactions. In
a large number of addition and condensation
reactions butyraldehydes react with themselves
or other carbonyl compounds, amines, alcohols,
nitriles, and other functional groups. On an in-
dustrial scale, the most important synthesis of
this kind is the homocondensation of n-butyral-
dehyde in the presence of a basic catalyst. The
initially formed 2-ethylhexenal is converted by
hydrogenation to 2-ethylhexanol, the alcohol
component of the most important PVC plasticiz-
er, dioctyl phthalate (DOP) [1], [3–5], [40], [41].
Mild reaction conditions during the aldolization
step allow butyraldol (2-ethyl-3-hydroxyhexa-
nal)to be isolated, which can be hydrogenated
to 2-ethyl-1,3-hexanediol.
Vol. 6
Figure 1. Reactions of butyraldehydes
The condensation product of n-butyralde-
hyde,2-ethylhexenal, also is selectively hydroge-
nated in the presence of a precious metal catalyst
to yield 2-ethylhexanal, which is converted to 2-
ethylhexanoic acid or 2-ethylhexylamine [1],
[3–5], [40].
Condensation of n-butyraldehyde with two
moles of formaldehyde and subsequent hydro-
genation yields trimethylolpropane [1], [42],
[43]. Phenol and n-butyraldehyde condense to
yield oil-soluble paints, and condensation pro-
ducts with urea are used in alcohol-soluble paints
[1].
Condensation of n-butyraldehyde with acet-
aldehyde gives 2-ethylbutyl products [44]; their
properties and applications are described in
[45].
With poly (vinyl alcohol) n-butyraldehyde
condenses to poly (vinyl butyral), PVB, which
is used in the manufacture of laminated safety
glass or as a bonding agent in paints [1].
Butanals 403
Condensation products of n-butyraldehyde
with aniline, butylamine, thiourea, diphenylgua-
nidine, or methylthiocarbamate are used on a
large scale as vulcanizing accelerators for rubber
[1].
Reductive amination, that is, the reaction with
hydrogen and ammonia or amines, provides
access to primary, secondary, and tertiary buty-
lamines [1], [46–48].
The homocondensation of isobutyraldehyde
leads via the intermediate isobutyraldoxane (4-
hydroxy-5,5-dimethyl-2,6-diisopropyl-1,3-diox-
ane) to isobutyraldol or secondary products such
as 2,2,4-trimethylpentane-1,3-diol, 2,2,4-tri-
methylpentane-1,3-diol mono- and diisobutyrate,
and 2,2,4-trimethylpentane-1-ol [1], [49–52].
The reaction of isobutyraldehyde with form-
aldehyde forms primary hydroxypivalaldehyde,
a starting material for products with a neopentyl
backbone. Especially neopentyl glycol, obtained
by hydrogenation of hydroxypivalaldehyde, has
404 Butanals
become increasingly important [53], [54]. The
wide variety of its uses is described in [55].
D,L-Hydroxy-b,b-dimethylbutyrolactone
(pantolactone), is obtained by reaction of isobu-
tyraldehyde, formaldehyde, and sodium cyanide
[1], [56], [57].
The reaction of isobutyraldehyde with urea
produces slow-release fertilizers (! Fertilizers,
1. General) [1]. Isobutyraldehyde serves as a raw
material for the syntheses of the amino acids D,L-
valine and D,L-leucine [1].
The Tishchenko reaction is used to obtain
isobutyl isobutyrate, a specialty solvent. Acetals
of the butyraldehydes with various alcohols serve
as solvents for cellulose, resins, and rubber [1],
[54].
The crossed Tishchenko reaction of n-butyr-
aldehyde with acetaldehyde provides commer-
cial ester mixtures. Butyraldehydes and hydrox-
ylamine yield the corresponding aldoximes or
their salts [1], [54].
Other Reactions. Isobutyraldehyde can be
isomerized to n-butyraldehyde and methyl ethyl
ketone or converted to diisopropyl ketone [1],
[54]. The chlorination of butyraldehydes yields
fragrances and pharmaceutical intermediates [1],
[54], [58–60]. n-Butyraldehyde is used as a cata-
lyst component for special polymerization reac-
tions [61–64]. Isobutyraldehyde can be con-
verted to isobutene on special molybdenum cat-
alysts [65].
Additional reactions and applications can be
found in [1], [54] and references therein.
7. Toxicology
Butyraldehydes have low acute toxicity (Ta-
ble 5). Exposure limits have not yet been estab-
lished. Butyraldehyde liquids and vapors strong-
ly irritate the skin, eyes, and respiratory organs,
possible due to rapid oxidation to the carboxylic
acids on contact with air. The symptoms are
coughing, watering eyes, and a burning sensation
on the skin and in the nose and throat. On
exposure to higher doses, the CNS is impaired,
resulting in depression, dizziness, headaches,
and a slight narcotic effect. The repugnant smell
of butyraldehydes occasionally causes nausea
and vomiting. Subcutaneous injection of n-bu-
tyraldehyde causes hemolysis.
Vol. 6
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21 Hoechst AG: Katalysatoren Hoechst, Frankfurt 1979,
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22 C. D. Frohning et al. in J. Falbe (ed.); Chemierohstoffe aus
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23 Hoechst AG: Delivery specifications, Frankfurt 1984.
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24 Ruhrchemie AG, DE 2905267, 1981 (J. Weber, V. Falk,
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25 Allied Chem. Corp., US 2808429, 1954.
26 Universal Oil Prod. Co., US 2683174, 1949.
27 V. M. Polyakov et al., Khim. Promst. (Moscow) 1972,
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28 W. Rupilius in F. Korte (ed.): Methodicum Chimicum,
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29 J. Simonik, L. Beranek, J. Catal. 24 (1972) no. 2, 348.
30 C. E. Loeffler, L. Stautzenberger, I. D. Unruh, Encycl.
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31 Mitsubishi Chemical Industries Co. Ltd., DE-OS
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Noma); JP 78105412, 1977 (T. Maki); JP 78105413,
1977 (T. Maki); JP 7909203, 1977 (T. Maki); JP
78108915, 1977 (T. Maki).
Vol. 6
32 Chisso Corp., JP 7378116, 1973 (M. Fukin, T. Hirai, T.
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33 A. Benning, L. Mußler, H. Tummes in F. Korte (ed.):
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34 B. Lappe, E. Schulz, in B. Cornils, W. A. Herrmann (eds.):
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Otake).
36 Union Carbide Corp., DE-OS 2836309, 1979 (D. W.
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37 Chisso Corp., JP 7946705, 1979 (M. Fukui, N. Otake, N.
Nagata).
38 Johnson, Matthey PLC, GB 2094782, 1982 (E. Shutt).
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40 B. Cornils, A. Mullen, Hydrocarbon Process. 1980 (11)
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41 Ruhrchemie AG, DE-OS 2713434, 1978 (H. Tummes, H.
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42 Bayer AG, DE-OS 2702582, 1978 (O. Immel, H. H.
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43 L. Cairati et al., Chim. Ind. (Milan) 63 (1981) no. 11,
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44 Mitsubishi Chemical Industries Co., Ltd., JP 7424891,
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45 B. Cornils, H. Feichtinger, Chem. Ztg. 101 (1977) 107 –
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46 Texaco Inc., US 4299985, 1981 (J. F. Knifton, P. H.
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47 BASF AG, DE-OS 2725669, 1978 (K. Merkel et al.).
48 B. Cornils, H. Feichtinger in J. Falbe, U. Hasserodt (eds.):
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Thieme-Verlag, Stuttgart 1978, p. 45.
49 BASF AG, DE-OS 820518, 1979 (F. Merger, H. J.
F€
orster).
50 Eastman Kodak Co., US 4225726, 1980 (D. L. Morris, A.
W. McCollun).
51 Chisso Corp., JP 7715582, 1977 (J. Tsuchiya et al.); JP
7323411, 1973 (R. Takakashi, J. Tsuchiya); JP 7334574,
1973 (S. Matsumoto, K. Gunji, T. Hamahata).
52 Hoechst AG, DE-OS 3102826, 1982 (H. Baltes, E. J.
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53 Eastman Kodak Co., DE-OS 2652224, 1977 (B. W.
Palmer, H. N. Wright).
Butanals 405
54 H. J. Hagemeyer, G. DeCroes: The Chemistry of Isobu-
tyraldehyde and its Derivatives, Tennessee Eastman
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55 B. Cornils, H. Feichtinger, Chem. Ztg. 100 (1976) 504 –
514.
56 BASF AG, DE-OS 2758883, 1979 (H. Distler, W.
Goetze).
57 VEB-Jenapharm, GB 1345459, 1974 (J. Schmidt et al.);
DE-OS 2228641, 1973 (J. Schmidt, H. Grunert, C.
Weigelt).
58 Allied Chemical Corp., US 4096187, 1978 (J. H. Bonfield,
A. Murthy, D. Pickens).
59 Dow Chemical Co., US 3801645, 1974 (D. A. Dalman).
60 Shell International Research Maatschappij, DE-OS
2641356, 1977 (A. Reinink, J. Grendelman).
61 Daicel Ltd., JP 7411480, 1974 (A. Tanaka et al.).
62 Thiokol Chemical Corp., DE 1545025, 1974 (R. M.
Gobran, S. W. Osborn).
63 Japan Synthetic Rubber Co. Ltd., DE-OS 2444681, 1975
(M. Ikeda et al.).
64 Ube Industries Ltd., DE-OS 2445776, 1975 (H. Ueno et
al.).
65 Toa Nenryo Kogyo K. K., JP 7748603, 1977 (K. Kaneko,
H. Furukawa).
Further Reading
R. Ballini (ed.): Eco-friendly Synthesis of Fine Chemicals,
Royal Society of Chemistry, Cambridge, UK 2009.
E. Billig: Butyraldehydes, ‘‘Kirk Othmer Encyclopedia of
Chemical Technology’’, 5th edition, John Wiley & Sons,
Hoboken, NJ, online DOI: 10.1002/
0471238961.0221202502091212.a02.pub2.
G. P. Chiusoli, P. M. Maitlis (eds.): Metal-Catalysis in
Industrial Organic Processes, Royal Society of Chemis-
try, Cambridge, UK 2006.
B. H. Davis, M. L. Occelli (eds.): Advances in Fischer-
Tropsch Synthesis, Catalysts, and Catalysis, CRC Taylor
& Francis, Boca Raton, FL 2010.
L. Koll
ar (ed.): Modern Carbonylation Methods, Wiley-
VCH, Weinheim 2008.
P. W. N. . v. Leeuwen: Homogeneous Catalysis, Kluwer
Academic Publishers, Dordrecht 2008.
R. Mahrwald: Aldol Reactions, Springer, Dordrecht 2009.
G. Tojo, M. Fernandez: Oxidation of Alcohols to Aldehydes
and Ketones, Springer, New York, NY 2006.