Butanediols, Butenediol, and Butynediol 1

Butanediols, Butenediol, and Butynediol

Heinz Gräfje, BASF Aktiengesellschaft, Ludwigshafen, Federal Republic of Germany (Chap. 1.1)
Wolfgang Körnig, BASF Aktiengesellschaft, Ludwigshafen, Federal Republic of Germany (Chap. 1.2)
Hans-Martin Weitz, BASF Aktiengesellschaft, Ludwigshafen, Federal Republic of Germany (Chap. 1.3)
Wolfgang Reiß, BASF Aktiengesellschaft, Ludwigshafen, Federal Republic of Germany (Chap. 1.3)
Guido Steffan, Bayer AG, Leverkusen, Federal Republic of Germany (Chap. 2.1)
Herbert Diehl, Bayer AG, Leverkusen, Federal Republic of Germany (Chap. 2.1)
Horst Bosche, BASF Aktiengesellschaft, Ludwigshafen, Federal Republic of Germany (Chap. 2.3)
Kurt Schneider, BASF Aktiengesellschaft, Ludwigshafen, Federal Republic of Germany (Chap. 2.3)
Heinz Kieczka, BASF Aktiengesellschaft, Ludwigshafen, Federal Republic of Germany (Chap. 3)

1. 1,4-Diols . . . . . . . . . . . . . . . . . . . 1 2.1. 2,3-Butanediol . . . . . . . . . . . . . . . 6

1.1. 2-Butyne-1,4-diol . . . . . . . . . . . . . . 1 2.2. 1,3-Butanediol . . . . . . . . . . . . . . . 7
1.2. 2-Butene-1,4-diol . . . . . . . . . . . . . . 3 2.3. 1,2-Butanediol . . . . . . . . . . . . . . . 7
1.3. 1,4-Butanediol . . . . . . . . . . . . . . . 4 3. Toxicology . . .. . . . . . . . . . . . . . . 7
2. Other Butanediols . . . . . . . . . . . . . 6 4. References . . .. . . . . . . . . . . . . . . 8

1. 1,4-Diols Substitution of the hydroxyl groups is anal-

ogous to that of other diols. In the case of
1.1. 2-Butyne-1,4-diol substitution by halogens very reactive com-
pounds are formed. The reaction with bifunc-
Physical Properties. 2-Butyne-1,4-diol tional compounds leads to linear polymers only.
[110-65-6], HOCH2 −C≡C−CH2 OH, M r The carbon – carbon triple bond undergoes the
86.09, mp 58 ◦ C, bp 150 ◦ C (at 1.8 kPa), is usual addition reactions of acetylene. Two moles
a colorless, hygroscopic, orthorhombic crys- of chlorine, but only one mole of bromine or
talline compound, which is readily soluble in iodine, are added per mole of diol. Chlorina-
water (374 g in 100 g at 25 ◦ C) and in strongly tion in the presence of hydrochloric acid gives
polar solvents, e.g., alcohol, acetone, but only 2,3-dichloro-3-formylacrylic acid (mucochloric
slightly soluble in ether and almost insoluble in acid) [87-56-9]:
hydrocarbons.
Heat of vaporization 50.28 kJ/mol, 584 kJ/kg
(at 101.3 kPa)
Heat of combustion 2204 kJ/mol, 25.5 kJ/g
Flash point (DIN 51758) 152 ◦ C
Ignition point 335 ◦ C The addition of water, catalyzed by mer-
cury salts, leads to the rather unstable 2-
oxobutanediol.
Chemical Properties. 2-Butyne-1,4-diol
decomposes relatively slowly between 160 and Production. The synthesis of 2-butyne-1,4-
200 ◦ C, but at temperatures significantly above diol, based on the work of Reppe and his cowork-
200 ◦ C violent decomposition can occur. Explo- ers [1–3], is carried out by reaction under pres-
sive decomposition can be caused or accelerated sure of acetylene and an aqueous solution of
by alkali hydroxide, strong anhydrous acids, and formaldehyde, catalyzed by copper acetylide:
certain heavy-metal salts, particularly those of 2 CH2 O + HC≡CH
mercury. 2-Butyne-1,4-diol is sensitive to oxi- −→ HOCH2 −C≡C−CH2 OH ∆H
dation. =−100.5 kJ/mol

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

10.1002/14356007.a04 455
2 Butanediols, Butenediol, and Butynediol
This reversible reaction proceeds via propar-
gyl alcohol, 2-propyn-1-ol [107-19-7], which
mostly remains on the catalyst and thus only-
partially goes into solution. The reaction is first
order in respect to formaldehyde and, in indus-
trial processes, effectively zero order in respect
to acetylene.
The prime objective in the synthesis is to min-
imize the formaldehyde concentration in the re-
sulting butynediol solutions. In principle, it is
possible to react rather concentrated formalde-
hyde solutions partially, distill off the unreacted
formaldehyde under pressure, and reintroduce it
into the reactor. However, this process is com-
plex and detrimental to the catalyst. Usually, the
production of the butynediol is carried out con-
tinuously in cascades of three to five reactors.
In these reactors the catalyst is present either as
a fixed bed of strands 3 – 5 mm in diameter and
10 mm in length (Fig. 1) or as a fluidized bed
of particles of diameter 0.1 – 2 mm. In the first
case the formaldehyde solution, together with
gaseous acetylene, is fed from the top [4]. In
the fluidized-bed process the required amount
of acetylene is dissolved in the solution and the
solution is then fed from the bottom, suspending
the catalyst (Fig. 2) [5].
Figure 1. Synthesis of butynediol, fixed-bed reactor
a) Liquid seal pump; b) Cooler; c) Reactor; d) Recycle
pump; e) Gas – liquid separator
In either case the reactors are equipped with
liquid-circulating systems. In the fixed-bed pro-
cess the volume of the liquid is determined by
external cooling. In the fluidized-bed process the
volume of the circulating liquid is determined by
the amount of acetylene which is introduced by
absorbing columns or injectors.
The catalyst is 3 – 6 % bismuth(III) oxide
and 10 – 20 % copper(II) oxide mostly sup-
ported on silica. Copper(II) oxide is converted
by acetylene and formaldehyde at 60 – 90 ◦ C
to copper(I) acetylide, which complexes fur-
ther acetylene [6] and thus forms the catalyst
proper. Bismuth oxide inhibits the formation
of water-insoluble polymers, the “cuprenes”,
from oligomeric acetylene complexes. Con-
ditions of synthesis: 80 – 100 ◦ C; 30 – 50 %
aqueous formaldehyde solution; partial pressure
of acetylene 2 – 6 bar, pH 5 – 8. Dilute alkali is
added to the cycle solution to adjust the pH.
Figure 2. Synthesis of butynediol, fluidized-bed reactor
a) Liquid seal pump; b) Recycle pump; c) Air cooler; d) Re-
actor
The product solution contains 33 – 55 % bu-
tynediol, 1 – 2 % propargyl alcohol, 0.4 – 1 %
unreacted formaldehyde, and 1 – 2 % byprod-
ucts. These byproducts are mainly high-boiling
materials, along with some sodium formate. The
butynediol can be recovered from this solution
by vacuum distillation; the propargyl alcohol is
recovered in an azeotrope.
Handling of High-Pressure Acetylene.
Acetylene can explode or even detonate if the
pressure rises above 1.4 bar (→ Acetylene). In
butynediol plants this deflagration is often ig-
nited by copper acetylide that was accidentally
deposited in the head space; if it dries up, it can
explode even upon slight vibration. Because
other sources of ignition can never be excluded
special precautions are required when handling
acetylene at pressures above 1.4 bar. When fill-
ing all equipment with metal packings and all
pipes with bundles of thin tubes (max. diame-
ter 12.5 mm) the transition from deflagration to
detonation (50 – 100 fold increase in pressure)
can be excluded. Explosion (10 – 12 fold in-
crease in pressure), however, cannot completely
be avoided; this is accounted for by planning
a 12-fold pressure for the whole apparatus [1].
When planning such plants the technical rules
 Butanediols, Butenediol, and Butynediol
for handling acetylene [7] and the publication
of Sargent [8] are recommended.
Environmental Protection. The off-gas,
which mainly consists of acetylene and other
hydrocarbons, is burnt. Waste-water problems
arise when regenerating the catalyst. The wa-
ter used for rinsing is treated biologically after
traces of catalyst have been deposited. Spent
catalyst must always be wet. Copper and bis-
muth can be recovered from the catalyst by acid
treatment.
Analysis. Because of the high boiling points
and the instability of the compounds involved,
GC analysis is of limited value only. The deter-
mination of byproducts by titration or by frac-
tional distillation (and subsequent GC analysis
of the fractions) is time consuming but more re-
liable.
Storage and Transportation. The storage
temperature should be kept below 40 ◦ C and
storage times longer than a few months should
be avoided because the butynediol flakes tend to
set up.
Uses. Approximately 95 % of the butyne-
diol is hydrogenated in aqueous solution to 1,4-
butanediol and occasionally to 2-butene-1,4-
diol. In addition, butynediol is an intermediate
for the production of 3-chloro-2-butynyl N- (3-
chlorophenyl)carbamate, a herbicide. Solvay re-
acts butynediol with alkylene oxides and ob-
tains a flame retardant after subsequent addi-
tion of bromine to the triple bond. Consider-
able amounts of butynediol are added to electro-
plating baths (nickel and copper) as brightening
agent. In steel inhibitor picklings, the diol acts
as a corrosion inhibitor.
Commercial Products. Butynediol is traded
as 34 % aqueous solution by GAF and BASF
(Golpanol BOZ liquid or Korantin BH liquid
with hexamethylenetetramine being added to the
latter). The anhydrous product is also traded as
flakes. Products containing residues (GAF) are
97 – 98 % pure. Distilled butynediol (BASF) is
99 % pure: Butynediol pure cryst., Korantin BH
solid, Golpanol pure solid.
3
1.2. 2-Butene-1,4-diol
Physical Properties. 2-Butene-1,4-diol
[110-64-5],
HOCH2 −CH=CH−CH2 OH,C4 H8 O2 , Mr
88.1, mp 10 ◦ C, bp 240 ◦ C (at 1013 mbar), bp
140 ◦ C (at 24 mbar), is a pale yellow liquid,
which is soluble in water. The product should
be distilled at reduced pressure because it dete-
riorates above 180 ◦ C.
Specific heat capacity 2.71 J g−1 K−1
Flash point 127 ◦ C
Ignition temperature 335 ◦ C
Vapor pressure
t, ◦ C 110.4 123.7 140 171.3 240
p,mbar 4.4 9.6 24 101.7 1013
Chemical Properties. Butenediol under-
goes the typical reactions of alcohols, such as
ester formation with anhydrides or acid chlo-
rides, substitution of the hydroxyl groups by
halogen, and the formation of polyesters with di-
carboxylic acids. Typical reactions of the double
bond are addition of halogen, epoxidation with
hydrogen peroxide, copolymerization with vinyl
esters, and the classic Diels-Alder reaction with
dienes, e.g., with hexachlorocyclopentadiene.
Production. 2-Butene-1,4-diol is produced
industrially by partial hydrogenation of 2-
butyne-1,4-diol in aqueous solution and in the
presence of a palladium catalyst, which gener-
ally is poisoned with zinc or other metals [9]. The
main product of this synthesis is cis-2-butene-
1,4-diol. Raney nickel can also be used as a cata-
lyst for the hydrogenation [10]. Another method
for the production of 2-butene-1,4-diol is the
acetoxylation of butadiene followed by hydrol-
ysis [11].
Analysis. The 2-butene-1,4-diol concentra-
tion in the product is determined by gas chro-
matography, the water content by the Karl Fis-
cher method.
Storage and Quality. 2-Butene-1,4-diol
must be stored in rust-free containers. Typical
commercial specifications are: purity 98.5 %,
mp 10 ◦ C, color light to slightly yellow, water
content < 0.5 %.
4 Butanediols, Butenediol, and Butynediol
Uses. 2-Butene-1,4-diol is used for the pro-
duction of endosulfan, chlorinated bicyclo-
[2.2.1]heptene-(2)-bis(oxyalkylene-5,6) sulfite,
an insecticide [12]; for the production of pyri-
doxine (vitamin B6) [13]; and in mixtures with
other compounds as bactericide.
Economic Aspects. Worldwide 4000 – 5000 t/a
of 2-butene-1,4-diol are produced, most of
which is used for the production of crop protec-
tion products and vitamins.
1.3. 1,4-Butanediol
Physical Properties. 1,4-Butanediol
[110-63-4], HOCH2 CH2 CH2 CH2 OH,C4 H10 O2 ,
M r 90.12, is a colorless, almost odorless, hy-
groscopic liquid (see Table 1), readily soluble in
water, alcohols, ketones, glycol ethers, and gly-
col ether acetates, less soluble in diethyl ether
and esters, and not miscible with aliphatic and
aromatic hydrocarbons and chlorinated hydro-
carbons.
Chemical Properties. 1,4-Butanediol is
readily cyclized in acid medium to give tetra-
hydrofuran. Dehydrogenation in the presence of
copper – zinc – aluminum catalysts gives buty-
rolactone.
1,4-Butanediol reacts with monocarboxylic
acids to give diesters [14]. Esterification with
dicarboxylic acids and their derivatives leads to
partially crystalline, linear, thermoplastic poly-
meric esters [15], [16].
At ca. 200 ◦ C, 1,4-butanediol reacts with am-
monia or an amine over nickel or cobalt cata-
lysts and in the presence of hydrogen to give
pyrrolidine or pyrrolidine derivatives [17], [18].
Phosgene reacts with 1,4-butanediol at −5 ◦ C to
give the bis(chloroformate) of butanediol [19],
[20]. Acrylonitrile adds to 1,4-butanediol at 20 –
100 ◦ C and in the presence of catalytic amounts
of alkali to give 1,4-bis(2-cyanoethoxy)butane
[21]. Like other alcohols, 1,4-butanediol can be
vinylated, giving the divinyl ether [22].
Production. 1,4-Butanediol is made on a
large industrial scale by continuous hydrogena-
tion of the 2-butyne-1,4-diol [23] over modified
nickel catalysts [24], [25]. The one-stage flow
process is carried out at 80 – 160 ◦ C and 300 bar
according to Figure 3.
Figure 3. Hydrogenation of 2-butyne-1,4-diol
a) Piston pump; b) Preheater; c) Hydrogenation reactor;
d) Gas – liquid separator; e) Recycle compressor; f) Canned
motor pump; g) Hydrogen compressor; h) Air cooler
An aqueous solution of 2-butyne-1,4-diol
(30 – 50 %), together with carbon monoxide-free
hydrogen and recycled reaction mixture, which
acts as medium for dissipation of heat, is lead
over a reduced nickel – copper – manganese cat-
alysts on silica gel strands. The initial tempera-
ture in the reactor is 80 ◦ C; the temperature must
not exceed 170 ◦ C. In order to obtain a better
distribution of the liquid, hydrogen is also cir-
culated.
The raw product contains methanol,
propanol, and butanol as byproducts as well
as traces of 2-methyl-1,4-butanediol, hydroxy-
butyraldehyde, acetals, and triols. The reactor
effluent is worked up to pure 1,4-butanediol by
fractional distillation [26].
The hydrogenation of butynediol can also be
carried out in two process steps. In the first stage,
for example, at 40 bar, mainly 2-butene-1,4-diol
is obtained, which is then completely hydro-
genated at 300 bar in the second stage.
A further variant is the low-pressure hydro-
genation at ca. 20 bar over a suspended Raney
nickel catalyst, followed by hydrogenation at
120 – 140 ◦ C and 140 – 210 bar on a fixed-bed
contact [24].
Other Processes. 1,4-Butanediol can also be
made from raw materials other than acetylene.
Allyl alcohol and synthesis gas (CO + H2 ) can
 Butanediols, Butenediol, and Butynediol 5
Table 1. Physical properties of 1,4-butanediol

mp 20.2 ◦ C
bp 230.5 ◦ C (at 101.3 kPa)
Density
1.017 g/cm3 (at 20 ◦ C); 1.0154 g/cm3 (at 25 ◦ C)
Critical temperature tc 446 ◦ C
Critical pressure pc 41.2 bar
Vapor pressure: t, ◦ C 60 100 140 180 200
p, kPa ca. 0.031 0.47 4.08 21.08 41.5
Heat of fusion ∆H f 16.3 kJ/mol ± 5 %
Heat of vaporization: t, ◦ C 131.4 193.2 215.6 230.5
∆H v , kJ/mol 68.2 59.4 57.8 56.5
Specific heat capacity: t, ◦ C 20 50 100 150
c, J g−1 K−1 2.2 ± 2 % 2.46 ± 2 % 2.9 ± 3 % 3.33 ± 4 %
Specific heat capacity
of a 50 % aq. solution: t, ◦ C 20 50 75 100
c, J g−1 K−1 3.4 ± 2 % 3.56 ± 2 % 3.69 ± 2 % 3.82 ± 3 %
Heat of combustion ∆H c 2585 kJ/mol
◦
Thermal conductivity: t, C 30 50 70 100
λ, W m−1 K−1 0.2100 0.2091 0.2083 0.2069
Thermal conductivity
of a 50 % aq. solution: t, ◦ C 20 50 100 150
λ, W m−1 K−1 0.3601 0.3694 0.3886 0.3984
Viscosity η 91.56 mPa · s (at 20 ◦ C); 71.5 mPa · s (at 25 ◦ C)
Refractive index nD 1.4460 (at 20 ◦ C); 1.4446 (at 25 ◦ C)
Dielectric constant ε 31.4
Flash point 134 ◦ C

be converted to 1,4-butanediol according to a which can be madedirectly from butadiene ac-

process invented by Daicel [27], [28].
Mitsubishi uses a three-step process [29],
[30]: (1) the catalytic reaction of butadi-
ene and acetic acid yields 1,4-diacetoxy-2-
butene [18621-75-5]; (2) subsequenthydrogena-
tion gives 1,4-diacetoxybutane; and (3) hydrol-
ysis leads to 1,4-butanediol:
cording to a process developed by Chevron [35]:
1,2-epoxy-3-butene is made from butadiene and
a peroxide and subsequent isomerization yields
2,5-dihydrofuran [1708-29-8], whichis hydro-
genated to tetrahydrofuran:

Other products derived from 1,4-butanediol

BASF also has patented a similar process,
in which acetic acid first adds to butadiene;
the product then isomerizes to 1,4-diacetoxy-2-
butene [31], [32].
According to a process practiced by Toyo
Soda [33] chlorine first adds to butadiene to form
a mixture of 1,4-dichloro-2-butene [764-41-0]
and 3,4-dichloro-1-butene [760-23-6]. This
mixturereacts with sodium acetate to form 1,4-
diacetoxy-2-butene, which is subsequentlyhy-
drogenated directly to 1,4-butanediol.
In a patent described by Shell butadiene re-
acts with a peroxide to diperoxybutene, which is
then converted to 1,4-butanediol by hydrogena-
tion [34].
1,4-Butanediol also is a starting material for
the production of tetrahydrofuran [109-99-9],
are butyrolactone and tetrahydrofuran. In addi-
tion, both 1,4-butanediol and its derivatives are
used in the textile, leather, photographic, food,
and pharmaceutical industries.
The worldwide capacity for 1,4-butanediol is
ca. 512 000 t/a in 1995. European producers are
BASF and GAF/Chemische Werke Hüls; pro-
ducers in the United States are Du Pont, GAF,
and BASF Wyandotte. Whereas all these pro-
ducers use acetylene as starting material, a plant
at Mitsubishi Chemical Industries has been mak-
ing 1,4-butanediol from butadiene since 1982.
Storage and Quality. 1,4-Butanediol can be
stored indefinitely. The product is noncorrosive
and therefore can be transported in cast iron con-
tainers. When it is stored for longer periods, stor-
age tanks of steel or aluminum are necessary in
order to avoid traces of iron in the product. In
6 Butanediols, Butenediol, and Butynediol
this case, a cover of dry nitrogen also is recom-
mended. Typical commercial specifications are:
purity 99.5 – 99.8 %, mp 19.9 – 20.0 ◦ C.
Uses and Economic Aspects. 1,4-Butanediol
is a versatile intermediate for the chemical indus-
try. The most important area of application is the
production of polyurethanes and poly(butylene
terephthalate), → Polyurethanes. Among the
polyurethanes produced from 1,4-butanediol,
cellular and compact elastomers are of prime
importance. Poly(butylene terephthalate) is pro-
cessed particularly to plastic materials and hot-
melt adhesives, but is used also for the produc-
tion of plastic films and fibers.
2. Other Butanediols
2.1. 2,3-Butanediol
2,3-Butanediol [513-85-9], 2,3-butylene glycol,
exists in three stereoisomericforms:
Previously, 2,3-butanediol was obtained by
bacterial fermentation of hexoses and pentoses.
By pyrolysis of the diacetate very pure butadiene
can be obtained, which has been used in the
United States for the production of synthetic
rubber. Today butenes from crack gases are the
raw material.
Physical Properties. The 2,3-butanediols,
C4 H10 O2 , M r 90.12, are colorless and odorless,
strongly hygroscopic, oily liquids or crystals
with a sweet taste. They are miscible with water
and easily soluble in low molecular mass alco-
hols and ketones. For further physical data, see
Table 2.
Chemical Properties [36]. The dehydro-
genation of 2,3-butanediol yields acetoin
[513-86-0] and diacetyl [431-03-8]. Dehydra-
tion leads chiefly to 2-butanone. The oxidation,
e.g., with periodate, gives acetaldehyde; the re-
action can be used for analytical determination.
2,3-Butanediol forms cyclic esters, acetals, and
ketals. With diisocyanates, polyurethanes are
obtained.
Production. After removal of butadiene and
isobutene from crack gases, a C4 hydrocarbon
fraction, called C4 raffinate II, is obtained, which
contains approximately 77 % butenes and 23 %
of a mixture of butane and isobutane. By chloro-
hydrination of this fraction with a solution of
chlorine in water and subsequent cyclization
of the chlorohydrins with sodium hydroxide, a
butene oxide mixture of the following composi-
tion is obtained:
55 % trans-2,3-butene oxide, 30 % cis-2,3-
butene oxide, 15 % 1,2-butene oxide.
Hydrolysis of this mixture (50 bar, 160 –
220 ◦ C, reaction enthalpy ∆H = −42 kJ/mol)
yields a mixture of butanediols which are sepa-
rated by vacuum fractionation. In order to avoid
the formation of polyethers during the hydrol-
ysis, an excess of water must be used. The
fractionation of the butanediols is easier than
that of the butene oxides. By this reaction se-
quence, meso-2,3-butanediol is obtained from
trans-2-butene via trans-2,3-butene oxide; the
racemic mixture of R,R- and S,S-2,3-butanediol
is formed analogously from cis-2-butene via cis-
2,3-butene oxide. For a discussion of stereo-
chemistry of this reaction, see also [37].
Analysis, Storage. The butanediol mixture
is analyzed best by GC (polyethylene glycol as
stationary phase).
Storage and transportation do not provide any
problems. However, the hygroscopicity of the
product requires some precautions.
Uses. 2,3-Butanediol (at least 80 % meso iso-
mer, the rest racemic mixture) is used as a cross-
linking agent for naphthalene-1,5-diisocyanate
 Butanediols, Butenediol, and Butynediol 7
Table 2. Physical properties of 2,3-butanediols

(R,S)- 2R, 3R- 2S, 3S- Racemate (R,R-

2,3-Butanediol 2,3-Butanediol 2,3-Butanediol and S,S-2,3-
Butanediol)

mp, ◦ C 35.5 – 36.5 19 7.6

bp (976 mbar), ◦ C 181.7 179 – 180 ∗ 179 – 182 ∗ 176.7
bp (13.16 mbar), ◦ C 83.5 77.3 – 77.4 75.3 – 75.6
d 25
4 0.9939 0.9873 0.9872
n25
D 1.43719 1.43095 1.4306 1.43109
[α]25
D −13.16◦ ∗ +11.8◦ ∗
viscosity (35 ◦ C), mPa · s 65.6 21.8
mp of bis(4-nitrobenzoates), ◦ C 193 – 193.5 143 – 143.5 128 – 128.5

∗ Theoretically bp and absolute amount of rotation of enantiomers should be the same.

in the production of specific hard-rubber prod- Chemical Properties. 1,2-Butanediol is a

ucts (Vulkollan). Derivatives of 2,3-butanediol
are important as insecticides (Sapecron: acetal
with N-methylcarbamate of salicylic aldehyde)
and as intermediates in the pharmaceutical in-
dustry. 2,3-Butanediols have some interest as
humectants and in the synthesis of polymers and
plasticizers.
typical glycol and readily forms acetals and
ketals; with dicarboxylic acids or anhydrides
polyesters are formed and with diisocyanates
polyurethanes.
Production. 1,2-Butanediol is synthesized
by addition of water to 1,2-epoxybutane
[106-88-7]:

2.2. 1,3-Butanediol
1,3-Butanediol [107-88-0], M r 90.12, bp
207.5 ◦ C (at 1013 mbar), bp 103 – 104 ◦ C (at
10 mbar), d 20 20
4 1.0053, nD 1.4410, is miscible
with water and ethanol. The molecule has one
center of chirality, and the data given above
refer to the racemate. (R)-(−)-1,3-Butanediol
[6290-03-5] has a specific rotation (ethanol) of
[α]25
D = −18.8 .
◦
1,3-Butanediol is produced as an intermedi-
ate in the manufacture of butadiene from acetal-
dol ( → Butadiene). This process has, however,
been abandoned by most companies. The com-
pound is mainly used as a component of special
polyester resins.
2.3. 1,2-Butanediol [38]
Physical Properties. 1,2-Butanediol [584-
03-2], C4 H10 O2 , M r 90.12, mp −50 ◦ C, bp
195 – 196.9 ◦ C (at 101.3 kPa), is a colorless liq-
uid, d 20 20
4 1.0023, nD 1.4382. The diol is misci-
ble with water in all proportions, readily soluble
in alcohols, slightly soluble in ethers and esters,
and insoluble in hydrocarbons. The dynamic vis-
cosity at 20 ◦ C is 73 mPa · s and the flash point
107 ◦ C.
The hydration reaction is exothermic (∆H=
−93 kJ/mol). A 10 to 20-fold molar excess of
water is used to suppress polyether formation.
The reaction is carried out either without a cat-
alyst at 160 – 220 ◦ C and 10 – 30 bar or in the
presence of catalysts below 160 ◦ C and only
slightly above atmospheric pressure. Sulfuric
acid or strongly acid ion exchange resins are
used as catalysts [38]. Depending on the excess
of water, selectivity is 70 – 92 %. Higher ethers
of 1,2-butanediol are formed as byproducts.
Uses. The field of application for 1,2-
butanediol is not very broad. It is used mainly as
a solvent and intermediate.
3. Toxicology
1,2-Butanediol and 1,3-Butanediol. The me-
dian lethal dose (LD50 ) of 1,2-butanediol is
16 g/kg (rat, oral) [39]; the corresponding value
of 1,3-butanediol is 29.6 g/kg [40], [41]. Re-
peated administration of 1,3-butanediol to rats
8 Butanediols, Butenediol, and Butynediol
(2 a, 10 wt % in the feed) and to dogs (2 a, 3 wt %
in the feed) did not reveal any toxic effects [42].
In high doses, 1,3-butanediol has a narcotic ef-
fect with a specific depressive effect on the cen-
tral nervous system [43], [44]. 1,3-Butanediol is
approved as a food additive by the U.S. Food
and Drug Administration [45].
2,3-Butanediol has an LD50 value of 8.9 g/kg
(mouse, oral) [40].
1,4-Butanediol, however, with an LD50 value
of 1.78 g/kg [39] or 1.5 g/kg [46] (both rat, oral)
should be classified as harmful according to the
EC Council Directive. The observed depressive
effect on the central nervous system is attributed
to the metabolite γ-hydroxybutyric acid.
None of the butanediol isomers either irri-
tate or sensitize the skin; however, they cause
strong (1,2-butanediol) to slight (1,3- and 1,4-
butanediol) eye irritation [39].
2-Butene-1,4-diol with an LD50 value of
about 860 mg/kg (rat, oral) is harmful. Eye and
skin irritation are not observed, even after pro-
longed contact. Rats could inhale air saturated
with 2-butene-1,4-diol at 20 ◦ C for 8 h without
showing any symptoms [46]. Repeated intake
by rats (5 % in the feed) led to death after 7 – 11
days; 30 % in the feed led to the animals’ death
after four days [47].
1-Butene-3,4-diol with an LD50 value of ap-
proximately 1.5 g/kg (rat, oral) is also harmful.
An 8-h inhalation of air saturated with the com-
pound at 20 ◦ C by rats does not lead to any ef-
fects. The animals’ skin was not irritated after
contact for several hours; however, irritation to
the eyes may occur.
2-Butyne-1,4-diol is to be classified as
“toxic” having an LD50 value of about
100 mg/kg (rat, oral). Strong irritation to the skin
– especially after contact for several hours – and
to the eyes were observed. An 8-h inhalation of
air saturated with the compound at 20 ◦ C by rats
did not lead to any adverse effects [46].
Neither TLV nor MAK values have been es-
tablished for the compounds cited above.
4. References
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DE-OS 2510089, 1975; DE-OS 2505749,
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 Butanediols, Butenediol, and Butynediol
30. Y. Tanabe, Hydrocarbon Process. 60 (1981)
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32. BASF, DE-OS 2454768, 1976.
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34. Shell Oil, US 4384146, 1983.
35. Chevron Research, US 3932468, 1976.
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Butanes → Hydrocarbons
9
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