HIGH-TEMPERATURE SYNTHESIS OF THIOPHENE
893
a KhL-6 chromatograph (7.5-m column packed with
REFERENCES
molecular sieves, carrier gas argon).
1. Deryagina, E.N. and Voronkov, M.G., Khim. Getero-
tsikl. Soedin., 2000, p. 3.
The thermolysis was carried out in a flow system
under atmospheric pressure; the reactor was a hollow
quartz tube (19 mm in diameter) with a 3-mm ring gap
between the tube wall and thermocouple pocket. The
length of the reaction zone was 250 mm. The quartz
tube was placed into a tube furnace with automatic
temperature control. Liquid reactants were supplied
with the aid of an automatic syringe sampler. The flow
rate of gases (nitrogen or acetylene) was controlled
manually using a rheometer. The thermolysis products
were trapped into cooled receivers. The contact time
was calculated from the volume of the reaction zone
and volume rate of the reactants in the gas phase at the
reaction temperature.
2. Deryagina, E.N., Sukhomazova, E.N., Levanova, E.P.,
Russavskaya, R.V., and Voronkov, M.G., Zh. Org.
Khim., 1993, vol. 29, p. 2315.
3. Voronkov, M.G., Deryagina, E.N., and Sukhomazo-
va, E.N., Khim. Geterotsikl. Soedin., 1981, p. 565.
4. Deryagina, E.N., Korchevin, N.A., Sukhomazova, E.N.,
Turchaninova, L.P., and Voronkov, M.G., Zh. Org.
Khim., 1990, vol. 26, p. 1225.
5. Voronkov, M.G., Deryagina, E.N., Amosova, S.V.,
Kuznetsova, M.A., Kryuchkov, V.V., and Trofi-
mov, B.A., Khim. Geterotsikl. Soedin., 1975, p. 1579.
6. Deryagina, E.N., Levanova, E.L., Sukhomazova, E.N.,
and Voronkov, M.G., Russ. J. Org. Chem., 1998,
vol. 34, p. 44.
The thermolysis of sulfide I alone was carried out
in a stream of nitrogen (1.2 l/h); compound I was sup-
plied at a volume rate of 3.2 ml/h.
7. Voronkov, M.G. and Deryagina, E.N., Russ. J. Gen.
Chem., 2001, vol. 71, p. 1835.
8. Deryagina, E.N., Korchevin, N.A., Sukhomazova, E.P.,
Russavskaya, N.V., and Levanova, E.P., Neftekhimiya,
1995, vol. 35, p. 472.
Joint thermolysis of sulfide I with acetylene (see
table, run no. 8). The reactor was preliminarily purged
with nitrogen and heated to 650°C. Sulfide I, 7.28 g
(0.046 mol), was supplied at a rate of 3.2 ml/h, and
acetylene was supplied at a rate of 1.2 l/h (reactant
ratio 1:2, contact time 21.5 s). After 105 min, 2.9 g of
a liquid product mixture was collected. It contained
1.73 g of thiophene, 0.12 g of benzothiophene, 0.22 g
of thienothiophenes, 0.09 g of isomeric bithienyls,
0.09 g of carbon disulfide, 0.25 g of benzene, and 0.4 g
of other aromatic hydrocarbons (GLC). Thiophene was
isolated by distillation. A fraction with bp 80–82°C
contained more than 98% of thiophene, nD20 = 1.5240
(1.5246 [11]). Joint thermolysis of sulfide I, disulfides,
and acetylene was carried out in a similar way.
9. Gilchrist, T.L., Heterocyclic Chemistry, Harlow, Essex,
England: Longman Scientific & Technical, 1992,
2nd ed. Translated under the title Khimiya getero-
tsiklicheskikh soedinenii, Moscow: Mir, 1996, p. 258.
10. Aleksandrov, V.N. and Emel’yanov, V.I., Otravlyayu-
shchie veshchestva (Poisonous Substances), Sokol’-
skii, G.A., Ed., Moscow: Voennoe Izd., 1990, p. 137.
11. Voronkov, M.G. and Deryagina, E.N., Usp. Khim.,
2000, vol. 69, p. 90.
12. Rabinovich, V.A. and Khavin, Z.Ya., Kratkii khimi-
cheskii spravochnik (Brief Chemical Reference Book),
Rabinovich, V.A., Ed., Leningrad: Khimiya, 1978,
p. 184.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 41 No. 6 2005