Butanals 1

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 . . . . . . . . . . . . . . . . . . 1 5. Handling, Storage, and Shipment . . . . 5

2. Physical Properties . . . . . . . . . . . . . . 1 6. Chemical Reactions and Applications . 5
3. Production . . . . . . . . . . . . . . . . . . . 2
7. Toxicology ................... 8
4. Stabilization, Testing, and Quality Spec-
ifications . . . . . . . . . . . . . . . . . . . . . 4 8. References . . . . . . . . . . . . . . . . . . . 8

1. Introduction 2. Physical Properties

Butanals are saturated aliphatic C4 aldehydes, n-Butyraldehyde and isobutyraldehyde are col-
C4 H8 O, M r 72.11. There are two isomers: orless, flammable liquids with a pungent pene-
the straight-chain butyraldehyde [123-72-8] trating odor. Their vapors have a narcotic effect
(butanal) and thebranched isobutyraldehyde and irritate the mucous membranes. Both iso-
[78-84-2] (2-methylpropanal, dimethylacet- mers are miscible with organic solvents, such as
aldehyde). alcohols, ethers, and benzene. The solubilities of
the butyraldehydes in water are collected in Ta-
ble 1. Some physical data of the butyraldehydes
are compiled in Table 2. Table 3 gives the com-
Butyraldehyde Isobutyraldehyde
position of some binary and ternary azeotropes.
Further physical properties are provided in [1],
[2], and [6].
Both aldehydes are found in minor concentra-
tions in various essential oils, in plants, as well as Table 2. Physical properties of butyraldehydes
in other natural substances [1], [2]. Both butyr- Butyraldehyde Isobutyr-
aldehyde and isobutyraldehyde are highly reac- aldehyde
tive intermediates that serve as versatile build-
Melting point, ◦ C − 97 − 66
ing blocks for many chemical syntheses, pre- Boiling point, ◦ C 74.8 64
dominantly for the preparation of C4 – C8 com- Density at 20 ◦ C, g/cm3 0.803 0.788
pounds. Refractive index n20D 1.3805 1.3730
Viscosity at 20 ◦ C, mPa s 0.45 0.45
The annual production volume of butyr- Specific heat capacity
aldehydes is several million tones worldwide. at 25 – 30 ◦ C, J g−1 K−1 2.123 2.544
The total production capacity for n-butanal is Heat of vaporization
at the boiling point, J/g 436 409
6.8 × 106 t with a demand of 5.9 × 106 t. The Heat of combustion, kJ/mol − 2478.7 − 2510
annual growth rate is estimated to be 2 – 4 %. Crit. pressure, mPa 4.06 ca. 4.3
Crit. density, g/cm3 0.259
Production on an industrial scale is performed Crit. temperature, ◦ C 248 ca. 267
exclusively by hydroformylation (→ Oxo Syn- Surface tension at 20 ◦ C, mN/m 24.6 24
thesis) [3–5]. World-scale plants such as those Dielectric constant at 20 ◦ C 14.9 13.5
Vapor pressure at 20 ◦ C, kPa 12 17
operated by BASF, Oxeno (Degussa-Hüls), Dipole moment (vapor), Debye 2.72
Celanese, and UCC have an annual output of Coefficient of expansion
at 20 – 30 ◦ C, K−1
(200 – 600) × 103 t. 0.0013 0.0014

c 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

10.1002/14356007.a04 447
2 Butanals
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 3. Azeotropic mixtures with butyraldehydes

Compound Compound Compound Boiling point Concentration

A B C of azeotrope, of B (C) in the
◦
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

3. Production with advantageous catalyst separation and op-

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.
Hydroformylation of Propylene. In the hy-
droformylation 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 Cn+1 aldehyde. Transition-
metal hydridocarbonyl complexes of the general
formula [HM(CO)x ] (M = Co, Rh, Ru) serve as a
homogeneous catalysts. On an industrial scale,
hydroformylation is carried out at 90 – 180 ◦ C
and 2.0 – 30 MPa [3–5].
Basically, all olefins, diolefins, or even func-
tionally substituted olefins may be used as raw
materials. On an industrial scale alkenes from
C2 to C18 are predominantly used. Propylene
has gained particular significance, being con-
verted to a mixture of n- and isobutyraldehyde.
Although the reaction medium is homogeneous
in most processes, a two-phase process (wa-
ter/organic solvent) has also been developed,
timized energy consumption.
Depending on the oxo catalyst, the reaction
conditions, and the process design, mixtures
of butyraldehydes with a n/iso ratio from 1/1
to 20/1 are obtained. In addition to the alde-
hydes, which constitute 90 – 98 % of the re-
action mixture, minor amounts of byproducts
and secondary products of the reactive butyr-
aldehydes are formed, such as butyl formate,
butanols, and aldehyde dimers, trimers, and con-
densation products [3–5].
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
hydrido rhodium or cobalt species the n/iso
ratio is usually poor. By addition of ligands
like triphenylphosphine (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 lig-
and 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 ac-
tive 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, Eastman) had developed their own ver-
sions of the cobalt process. For short-chain
olefins like propylene, the cobalt technology
has almost fully been substituted by rhodium-
based processes. Only for higher and in par-
ticular 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 com-
monly 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 sep-
aration is performed in a separate vessel in which
the aldehyde vapors are flashed off and the liq-
uid solution containing the rhodium catalyst is
recycled to the reactor. In this operating mode,
the aldehyde condensation products serve as a
solvent for the catalyst. However, the applica-
tion of all versions is mostly limited to propyl-
ene and butene hydroformylation. Many plants
have been converted from high-pressure cobalt
to LPO technology for new or additional butyr-
aldehyde (and thus butanol and 2-ethylhexanol)
capacity.
By the mid-1980s Ruhrchemie (now
Celanese) and Rhône-Poulenc developed
a two-phase process with a water-soluble
rhodium/TPPTS complex. The major advan-
tages are the simple and mild catalyst recycle,
the high n/iso ratio of ca. 20/1 and the beneficial
low energy consumption of the whole process
[3–5], [8].
Butanals 3
The fourth generation of oxo catalysts used
for the production of butyraldehyde and espe-
cially of higher aldehydes (and thus less impor-
tant 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 cata-
lyst decomposition, phosphine-modified cobalt
or rhodium catalysts are separated from the re-
action product by fast flash distillation. The less
volatile catalysts remain at the bottom and are re-
cycled to the hydroformylation reactor without
further treatment. However, optimized catalyst
lifetime and thus improved activity and selec-
tivity requires the discharge of a small portion
of the catalyst for workup and addition of fresh
catalyst.
In contrast to the homogeneous hydro-
formylation processes, the Ruhrchemie/Rhône-
Poulenc 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 synthe-
sis 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 or-
ganic aldehyde phase. The catalyst solution is
recycled to the reactor via a heat exchanger sys-
tem, which generates steam. This results in one
of the advantages of the two-phase technology:
the high energy efficiency. The P/Rh ratio is kept
above 20/1 to ensure an n/iso ratio of at least
95/5. Almost no rhodium is leached out of the
4 Butanals
water phase. The organic phase containing the
crude aldehydes is stripped with synthesis gas to
remove dissolved propylene, which is recycled
to the reactor. The raw aldehyde mixture is split
into iso- and n-butyraldehydes in a distillation
unit.
Hydrogenation of Crotonaldehyde. Be-
fore the discovery of the hydroformylation re-
action, the aldol condensation of acetaldehyde
to give crotonaldehyde followed by hydrogena-
tion to n-butyraldehyde was the most important
method of producing n-butyraldehyde.
n-Butanol is formed as a byproduct by hy-
drogenation of the aldehyde moiety during the
selective hydrogenation of the double bond of
crotonaldehyde. Selective hydrogenation is per-
formed in gas- or liquid-phase processes. Typi-
cal catalysts applied are supported catalysts on
the basis of Cu, Ni, Pd, Ru, Fe, Cr, or Mn [1],
[9–14].
Up to the 1950s this route was still the pre-
ferred method for producing n-butyraldehyde
[15] on an industrial scale, but the convenient
one-stage oxo processes replaced crotonalde-
hyde hydrogenation almost completely. Only
countries with massive ethanol production based
on natural resources, such as Brazil, might redis-
cover the crotonaldehyde route for producing n-
butyraldehyde [15].
Dehydrogenation of Butanols. Butanols
formed in other processes, such as
Fischer – Tropsch synthesis [16], alcoholic fer-
mentation of sugar with Clostridium saccha-
robutylacetonium liquefaciens or Bacillus amy-
lobacter [17], and Reppe carbonylation [18],
can be dehydrogenated to butyraldehydes.
CH3 CH2 CH2 CH2 OH
CH3 CH2 CH2 CHO + H2
The reaction is carried out in the gas phase with
a heterogeneous catalyst [19]. The addition of
hydrogen acceptors such as O2 , either pure or as
air, increases the aldehyde yield but also the for-
mation of byproducts. Zinc- and/or chromium-
doped copper catalysts are particularly effective
[20], [21].
Fischer – Tropsch synthesis generates
small amounts of n-butyraldhyde, which is of
importance in some local markets [16], [22].
4. Stabilization, Testing, and Quality
Specifications
Stabilization. The reactivity of butanals is
determined by the polarity of the carbonyl group.
The inductive effect of the carbonyl group pro-
motes α-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,
storage and shipment only under the following
precautions:
Inert
– gas atmosphere for all reaction and work-up
steps
Storage
– with exclusion of UV light
Storage
– at constant and moderate temperature
Conversion
– into thermally stable compounds like
acetals, which are easily cleaved back to the
aldehydes
Addition
– of stabilizers and antioxidants
Testing. The most important method of test-
ing and continuous control of product quality
(Table 4) is gas chromatography with a low in-
jection temperature to avoid decomposition of
impurities, e.g., aldols.
In the analysis of butyraldehydes it is im-
portant to detect trimeric aldehydes, which are
formed readily, especially in the absence of sta-
bilizers. Since these trimerization reactions are
catalyzed by acids, contact with acidic com-
pounds must be strictly avoided during the
course of aldehyde processing. During the anal-
ysis of water in butyraldehyde by Karl Fischer
titration, special precautions must be taken to
avoid condensation to acetals, which is accom-
panied by formation of water. This is achieved
by the use of a solvent mixture composed of
four parts pyridine and one part ethylene glycol.
The density and refractive index of the water-
containing product are strongly affected by the
 Butanals 5
Table 4. Delivery specifications for butyraldehydes [23]

Method Butyraldehyde Isobutyraldehyde

moist dry moist dry

Butyraldehyde, wt % GLC
96.0
99.0  0.5  0.2

Isobutyraldehyde, wt% GLC  0.3
95.0
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  15  10  15  15
Acid number, mg KOH/g DIN 53402, ASTM D 1613  3.0 2  3.0  2.0
Water, wt% Karl Fischer  3.0  0.2  2.0  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 ◦ C)

equilibrium hydrate concentration, which is es- 6. Chemical Reactions and

tablished slowly. During determination of the
acid number care must be taken to exclude atmo-
spheric oxygen. The boiling point of the butyr-
aldehydes is strongly affected by traces of water.
Quality Specifications. Table 4 outlines the
standard quality specifications for butyr-
aldehydes. The limits are largely determined by
the intended use and by specific customer re-
quests.
5. Handling, Storage, and Shipment
The butyraldehydes are stored and shipped
in containers of corrosion-resistant steel, alu-
minum, glass, or ceramic, as well as specially
coated tanks of normal steel and drums with re-
movable polyethylene inserts. Even with water
contents below 0.1 % and storage under inert
gas, n-butyraldehyde dissolves iron from steel,
causing 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 addi-
tion of a suitable amine (e.g., triethanolamine)
or other bases [24].
Owing to the low flash points and ignition
temperatures (Table 5) as well as the high volatil-
ity 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 trans-
port must be observed (Table 5).
Applications
Owing to their reactivity butyraldehydes are im-
portant starting materials for a broad variety of
products [30]. Due to the high reactivity of the
carbonyl group, aldehydes undergo many or-
ganic chemical reactions. Typical aldehyde re-
actions are:
– Addition to the C=O bond without substitu-
tion of the oxygen atom
– Addition to the C=O 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 in-
dustrial scale.
Butyraldehydes are important intermediate
products for a vast number of C4 prod-
ucts, including n-butanol, n-butyric acid, n-
butylamines, and butyl acrylates, as well as
for the plasticizer alcohol 2-ethylhexanol (C8 )
and for C6 products 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,
Chap. 3.3.).
Hydrogenation. The butyraldehydes are
converted to the corresponding butanols by
catalytic hydrogenation, whereby both liquid-
phase and gas-phase processes are used. The
6 Butanals
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.

mild, highly selective gas-phase hydrogenation Addition and Condensation Reactions. In

is carried out on nickel or copper supported
catalysts.
Oxidation. Pure oxygen or air converts
butyraldehydes 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].
a large number of addition and condensation
reactions butyraldehydes react with themselves
or other carbonyl compounds, amines, alco-
hols, nitriles, and other functional groups. On
an industrial scale, the most important synthe-
sis of this kind is the homocondensation of n-
butyraldehyde in the presence of a basic cata-
lyst. The initially formed 2-ethylhexenal is con-
verted by hydrogenation to 2-ethylhexanol, the
alcohol component of the most important PVC
plasticizer, dioctyl phthalate (DOP) [1], [3–5],
[40], [41]. Mild reaction conditions during the
aldolization step allow butyraldol (2-ethyl-3-
hydroxyhexanal) to be isolated, which can be
hydrogenated to 2-ethyl-1,3-hexanediol.
The condensation product of n-butyr-
aldehyde, 2-ethylhexenal, also is selectively
hydrogenated 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

Figure 1. Reactions of butyraldehydes
yield oil-soluble paints, and condensation prod-
ucts 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].
Condensation products of n-butyraldehyde
with aniline, butylamine, thiourea, diphenylgua-
nidine, or methylthiocarbamate are used on a
large scale as vulcanizing accelerators for rub-
ber [1].
Reductive amination, that is, the reaction with
hydrogen and ammonia or amines, provides ac-
cess to primary, secondary, and tertiary buty-
lamines [1], [46–48].
The homocondensation of isobutyraldehyde
leads via the intermediate isobutyraldox-
Butanals 7
ane (4-hydroxy-5,5-dimethyl-2,6-diisopropyl-
1,3-dioxane) to isobutyraldol or secondary
products such as 2,2,4-trimethylpentane-1,3-
diol, 2,2,4-trimethylpentane-1,3-diol mono- and
diisobutyrate, and 2,2,4-trimethylpentane-1-ol
[1], [49–52].
The reaction of isobutyraldehyde with
formaldehyde forms primary hydroxypival-
aldehyde, a starting material for products with a
neopentyl backbone. Especially neopentyl gly-
col, obtained by hydrogenation of hydroxypival-
aldehyde, has become increasingly important
[53], [54]. The wide variety of its uses is de-
scribed in [55].
d,l-Hydroxy-β,β-dimethylbutyrolactone
(pantolactone), is obtained by reaction of
isobutyraldehyde, formaldehyde, and sodium
cyanide [1], [56], [57].
The reaction of isobutyraldehyde with urea
produces slow-release fertilizers (→ Fertilizers,
Chap. 4.4.2.2.) [1]. Isobutyraldehyde serves as a
8 Butanals
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. Ac-
etals of the butyraldehydes with various alco-
hols 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 catalyst component for special polymerization
reactions [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 es-
tablished. Butyraldehyde liquids and vapors
strongly irritate the skin, eyes, and respiratory
organs, possible due to rapid oxidation to the
carboxylic acids on contact with air. The symp-
toms are coughing, watering eyes, and a burn-
ing 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 re-
pugnant smell of butyraldehydes occasionally
causes nausea and vomiting. Subcutaneous in-
jection of n-butyraldehyde causes hemolysis.
8. References
1. Ullmann, 4th ed., 9, p. 42; Ullmann, 5th ed.,
A4, p. 447.
2. Kirk-Othmer, 3rd. ed., vol. 4, p. 376.
3. B. Cornils in J. Falbe (ed.): New Syntheses
with Carbon Monoxide, Springer Verlag,
Berlin-Heidelberg-New York 1980.
4. B. Cornils, E. Wiebus, CHEMTECH 25
(1995) no. 1, 33.
5. B. Cornils, Org. Proc. Res. &. Dev. 2 (1998)
no. 2, 121.
6. J. McGarry, Ind. Eng. Chem. 22 (1983) 313.
7. C. D. Frohning, C. W. Kohlpaintner in B.
Cornils, W. A. Herrmann (eds.): Homogeneous
Catalysis with Organometallic Compounds ,
VCH, Weinheim, 1996, pp. 29 – 104.
8. B. Cornils, W. A. Herrmann (eds.):
Aqueous-Phase Organometallic Catalysis,
Wiley-VCH, Weinheim 1998.
9. V. N. Kulakov et al., SU 172744, 1964.
10. Usines de Melle, DE 814444, 1949.
11. BASF AG, DE-OS 2839474, 1980; DE-OS
3130805, 1983 (M. Horner et al.).
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Butanals 9
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