TURAEVA, KURBATOV
1790
of the second fraction gave 0.1 g of Michler’s ketone.
The aqueous tetrahydrofuran solution was extracted
with hexane to isolate an additional amount of com-
pound IX, 2.5 g; overall yield 5.0 g (70%).
4,4'-bis(dimethylamino)benzophenone dipotassium
salt, we isolated 1.1 g (37%) of Schiff base IX,
mp 185–187°C (from acetone), Rf 0.42 (B), 0.1 g
(2.6%) of Crystal Violet (XI), Rf 0.1 (B), and 0.5 g
(18%) of alcohol X, mp 95°C. In the reaction with
4,4'-bis(dimethylamino)benzophenone dilithium salt,
we isolated 0.2 g (2%) of alcohol X, mp 185–187°C,
Rf 0.42,* 5.7 g (85%) of Michler’s ketone (VIII),
mp 173°C, and 1.9 g (87%) of aniline, Rf 0.82 (B).
Reaction of potassium bis(4-dimethylamino-
phenyl)ketyl (VIIIb) with aniline (II). The reaction
was carried out as described above for sodium deriva-
tive VIIIa. After addition of aniline, the originally blue
solution turned brown, and vigorous evolution of
hydrogen was observed. After 24 h, the mixture was
treated with water and extracted in succession with
hexane and benzene. Evaporation of the hexane extract
gave 2.5 g of a mixture of compound IX, Rf 0.42 (B)
and bis(4-dimethylaminophenyl)methanol (X), Rf 0.59
(B). A 0.5-g portion of this mixture was subjected to
column chromatography (see the preceding procedure)
to isolate 0.4 g of compound IX, mp 185–187°C (from
acetone), Rf 0.42 (B), overall yield 2.0 g (58%), 0.07 g
of alcohol X, mp 88–90°C (published data [14]:
mp 90°C), and 0.03 g of Crystal Violet (XI), Rf 0.1
(B). From the benzene extract we isolated traces of
Schiff base IX, overall yield 0.95 g (35%), and 0.6 g of
alcohol X, mp 95°C; published data [14]: mp 96°C.
REFERENCES
1. Kurbatova, A.S., Kurbatov, Yu.V., and Niyazova, D.A.,
Zh. Org. Khim., 1990, vol. 26, p. 649.
2. Turaeva, D.A., Kurbatov, Yu.V., and Muratova, G., Book
of Abstracts, 12th Int. Conf. on Organic Synthesis,
Venezia, Italy, 1998, p. 390.
3. Turaeva, D.A. and Kurbatov, Yu.V., Russ. J. Org.
Chem., 1999, vol. 35, p. 1092.
4. Turaeva, D.A., Kurbatova, A.S., and Kurbatov, Yu.V.,
Book of Abstracts, 10th IUPAC Symp. on Organo-
metallic Chemistry Directed towards Organic Synthesis,
Versailles, France, 1999, p. 490.
5. Turaeva, D.A. and Kurbatov, Yu.V., Russ. J. Org.
Chem., 2002, vol. 38, p. 1691.
The reaction of lithium bis(4-dimethylamino-
phenyl)ketyl (VIIIc) with aniline (II) was performed
as described above for sodium derivative VIIIa. We
isolated 0.2 g (2%) of alcohol X, mp 95°C, 5.7 g
(85%) of Michler’s ketone (VIII), mp 173°C (174°C
[14]), Rf 0.86 (B), and 1.9 g (87%) of aniline,
Rf 0.82 (B).
6. Turaeva, D.A., Cand. Sci. (Chem.) Dissertation,
Moscow, 1988.
7. Bachmann, V.E., J. Am. Chem. Soc., 1933, vol. 55,
p. 2827.
8. Okhlobystin, O.Yu., Perenos elektrona v organicheskikh
reaktsiyakh (Electron Transfer in Organic Reactions),
Rostov-on-Don: Rostov. Gos. Univ., 1974, p. 48.
Reactions of 4,4'-bis(dimethylamino)benzophe-
none disodium, dipotassium, and dilithium salts
with aniline (II). 4,4'-Bis(dimethylamino)benzophe-
none disodium, dipotassium, and dilithium salts were
prepared from 2.68 g (10 mmol) of Michler’s ketone
(VIII) and 20 mmol of the corresponding alkali metal
(cut in small pieces) in 100 ml of THF; the mixture
was kept in a hermetically closed flask until it became
homogeneous. After two weeks, a solution of 0.93 g
(10 mmol) of aniline in THF was added in a stream of
nitrogen to the resulting dark violet solution. The mix-
ture was then treated as described above for the
reactions of compounds VIIIa and VIIIb with aniline.
In the reaction with 4,4'-bis(dimethylamino)benzophe-
none disodium salt, we isolated 2.58 g (30%) of com-
pound IX, mp 185–187°C (from acetone), Rf 0.42 (B),
and 0.5 g of alcohol X, mp 95°C. In the reaction with
9. Foerst, W., Newer Methods of Preparative Organic
Chemistry, New York: Academic, 1963, p. 246.
10. Mendkovich, A.S. and Gul’tyai, V.P., Teoreticheskie
osnovy
khimii
organicheskikh
anion-radikalov
(Principles of the Chemistry of Organic Radical
Anions), Moscow: Nauka, 1990, p. 69.
11. Todres, Z.V., Ion-radikaly v organicheskom sinteze
(Radical Ions in Organic Synthesis), Moscow: Khimiya,
1986, p. 20.
12. Denisov, E.T., Kinetika gomogennykh khimicheskikh
reaktsii (Kinetics of Homogeneous Chemical Reac-
tions), Moscow: Vysshaya Shkola, 1978, p. 127.
13. Billman, J.H. and Tai, K.M., J. Org. Chem., 1958,
vol. 23, p. 535.
14. Spravochnik khimika (Chemist’s Handbook), Nikol’-
skii, B.P., Ed., Moscow: Khimiya, 1965, vol. 2, p. 476.
* As in Russian original.—Publisher.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 40 No. 12 2004