Butanediols, Butenediol, and Butynediol: 1. 1,4-Diols
Butanediols, Butenediol, and Butynediol: 1. 1,4-Diols
Butanediols, Butenediol, and Butynediol: 1. 1,4-Diols
Uses. 2-Butene-1,4-diol is used for the pro- process is carried out at 80 – 160 ◦ C and 300 bar
duction of endosulfan, chlorinated bicyclo- according to Figure 3.
[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.
1.3. 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
this case, a cover of dry nitrogen also is recom- and easily soluble in low molecular mass alco-
mended. Typical commercial specifications are: hols and ketones. For further physical data, see
purity 99.5 – 99.8 %, mp 19.9 – 20.0 ◦ C. Table 2.
Uses and Economic Aspects. 1,4-Butanediol Chemical Properties [36]. The dehydro-
is a versatile intermediate for the chemical indus- genation of 2,3-butanediol yields acetoin
try. The most important area of application is the [513-86-0] and diacetyl [431-03-8]. Dehydra-
production of polyurethanes and poly(butylene tion leads chiefly to 2-butanone. The oxidation,
terephthalate), → Polyurethanes. Among the e.g., with periodate, gives acetaldehyde; the re-
polyurethanes produced from 1,4-butanediol, action can be used for analytical determination.
cellular and compact elastomers are of prime 2,3-Butanediol forms cyclic esters, acetals, and
importance. Poly(butylene terephthalate) is pro- ketals. With diisocyanates, polyurethanes are
cessed particularly to plastic materials and hot- obtained.
melt adhesives, but is used also for the produc-
tion of plastic films and fibers. Production. After removal of butadiene and
isobutene from crack gases, a C4 hydrocarbon
fraction, called C4 raffinate II, is obtained, which
2. Other Butanediols contains approximately 77 % butenes and 23 %
of a mixture of butane and isobutane. By chloro-
2.1. 2,3-Butanediol hydrination of this fraction with a solution of
chlorine in water and subsequent cyclization
2,3-Butanediol [513-85-9], 2,3-butylene glycol, of the chlorohydrins with sodium hydroxide, a
exists in three stereoisomericforms: butene oxide mixture of the following composi-
Previously, 2,3-butanediol was obtained by tion is obtained:
bacterial fermentation of hexoses and pentoses. 55 % trans-2,3-butene oxide, 30 % cis-2,3-
By pyrolysis of the diacetate very pure butadiene butene oxide, 15 % 1,2-butene oxide.
can be obtained, which has been used in the 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].
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 The hydration reaction is exothermic (∆H=
10 mbar), d 20 20
4 1.0053, nD 1.4410, is miscible −93 kJ/mol). A 10 to 20-fold molar excess of
with water and ethanol. The molecule has one water is used to suppress polyether formation.
center of chirality, and the data given above The reaction is carried out either without a cat-
refer to the racemate. (R)-(−)-1,3-Butanediol alyst at 160 – 220 ◦ C and 10 – 30 bar or in the
[6290-03-5] has a specific rotation (ethanol) of presence of catalysts below 160 ◦ C and only
[α]25
D = −18.8 .
◦
slightly above atmospheric pressure. Sulfuric
1,3-Butanediol is produced as an intermedi- acid or strongly acid ion exchange resins are
ate in the manufacture of butadiene from acetal- used as catalysts [38]. Depending on the excess
dol ( → Butadiene). This process has, however, of water, selectivity is 70 – 92 %. Higher ethers
been abandoned by most companies. The com- of 1,2-butanediol are formed as byproducts.
pound is mainly used as a component of special
polyester resins. Uses. The field of application for 1,2-
butanediol is not very broad. It is used mainly as
a solvent and intermediate.
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 3. Toxicology
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-
1,2-Butanediol and 1,3-Butanediol. The me-
ble with water in all proportions, readily soluble dian lethal dose (LD50 ) of 1,2-butanediol is
in alcohols, slightly soluble in ethers and esters, 16 g/kg (rat, oral) [39]; the corresponding value
and insoluble in hydrocarbons. The dynamic vis- of 1,3-butanediol is 29.6 g/kg [40], [41]. Re-
cosity at 20 ◦ C is 73 mPa · s and the flash point peated administration of 1,3-butanediol to rats
107 ◦ C.
8 Butanediols, Butenediol, and Butynediol
30. Y. Tanabe, Hydrocarbon Process. 60 (1981) 40. L. Fischer et al., Z. Gesamte Exp. Med. 115
no. 9, 187. (1949) 22.
31. BASF, DE-OS 2444004, 1976. 41. A. Loeser, Pharmazie 4 (1949) 263.
32. BASF, DE-OS 2454768, 1976. 42. R. A. Scala et al., Toxicol. Appl. Pharmacol.
33. Toyo Soda, US 3720704, 1973. 10 (1967) 160.
34. Shell Oil, US 4384146, 1983. 43. G. D. Frye et al., J. Pharmacol. Exp. Ther. 216
35. Chevron Research, US 3932468, 1976.
(1981) 306.
36. Beilstein, 1 (3) 2178, 2180, 2181, 2183; 1 (4)
44. G. S. Stoewsand et al., Proc. Int. Congr. Nutr.
2524, 2525.
37. C. E. Wilson, H. J. Lucas, J. Am. Chem. Soc. 7th 1966 4 (1967) 1082–7.
58 (1936) 2396. 45. W. R. Hewitt et al., Toxicol. Appl. Pharmacol.
38. K. Szafraniak, J. Myszkowski, A. Zielinski, W. 64 (1982) 529.
Pyc, PL 79662, 1978; Chem. Abstr. 92 (1980) 46. BASF, unpublished results 1959 – 1981.
22031 n; Przem. Chem. 52 (1973) no. 11, 47. H. Schlüssel, Naunyn Schmiedebergs Arch.
744 – 746; Chem. Abstr. 80 (1974) 47385 w. Exp. Pathol. Pharmakol. 221 (1954) 67.
39. V. K. Rowe et al.: Patty’s Industrial Hygiene
and Toxicology, vol. 2 C, Wiley Interscience
Publ., New York 1982, p. 3874.
Butanes → Hydrocarbons