192
IDRISOVA
Bisamides X XVII were also obtained by reaction
The separated crystals were filtered off, washed with
acetone, and dried.
of monoamides VIII or IX with anhydrides IV VI or
VII in DMF at room temperature. Since monoamides
VIII, IX are insoluble in acetone, their reaction with
anhydrides IV VI or VII occurs only in DMF that
ensures homogeneity of the medium. The developed
procedure provides a possibility to obtain any mixed
bisamides by acylation of m- or p-phenylenediamine
varying the order of anhydride addition and the
solvent.
cis-4-Cyclohexene-1,2-dicarboxylic acid N-(m-
aminophenyl)amide (VIII). Yield 99%. mp 189 C
(from benzene). Rf 0.30. Found, %: C 64.05; H5.91;
N 10.21. C14H16N2O3. Calculated, %: C 64.62;
H 6.15; N 10.77.
cis-4-Cyclohexene-1,2-dicarboxylic acid N-(p-
aminophenyl)amide (IX). Yield 98%. mp 202 C
(from benzene). Rf 0.31. Found, %: C 63.91; H5.88;
N 10.29. C14H16N2O3. Calculated, %: C 64.62; H
6.15; N 10.77.
The proof of the structure of mixed bisamides
X XVII was performed by transformation thereof
into bisimides XVIII XXV by heating the respective
amides in DMF for 5 6 h at boiling (152 ). The
characteristics of bisamides X XVII and bisimides
XVIII XXV are given in the table.
Synthesis of mixed bisamides X XVII. (a) To a
solution of 0.1 mol of anhydride (I) and 0.1 mol of
anhydride IV VI or VII in 300 ml of acetone at room
temperature while vigorous stirring was added solu-
tion of 0.1 mol of meta-(II) or para-(IV) phenylene-
diamine in 50 ml of acetone. The mixture was left
standing for 12 h till crystals precipitated. The pre-
cipitate was filtered off, washed with acetone, dried,
and analyzed. The characteristics of bisamides X
XVII are given in table.
The structure of the mixed bisamides is also con-
firmed by IR spectra containing the stretching bands
1
of C=C bonds at 1660, 1610 cm and of amide
1
group at 3290, 3220 cm . The stretching vibrations
of the carboxy group appear as a strong shoulder at
1
1
1720 cm . The band at 2600 cm indicates that the
carboxy group is linked to the adjacent amide group
by an intramolecular hydrogen bond. The presence
of carboxy group in compounds X XVII was also
proved by measuring the acid numbers.
(b) To a vigorously stirred solution of 0.1 mol of
monoamide VIII or IX in 300 ml DMF was gradually
added at room temperature 0.1 mol of anhydride
IV VII dissolved in 50 ml of DMF. The mixture was
left standing for 12 h. The precipitated crystals were
filtered off, dried, and recrystallized from benzene.
Yield of bisamides X XVII 96 99%. Characteristics
of compounds X XVII prepared along procedures
(a) and (b) are identical.
EXPERIMENTAL
IR spectra of bisamides X XVII were recorded on
spectrophotometer UR-20 from mulls in mineral
oil [3]. The acid numbers were determined by
potentiometric titration with the use of LPM-60M
device by procedure [4]. The purity of compounds
was checked by TLC on silica gel of L5/40 grade,
eluent benzene dichloroethane acetic acid, 4: 1.5 : 1
(by volume), visualizing of spots under UV irradia-
tion [5]. Molecular weight was determined by cryo-
scopy in camphor [6].
Synthesis of mixed bisimides XVIII XXV.
A mixture of 0.1 mol of mixed bisamide X XVII and
200 ml of DMF was heated to 152 C for 5 6 h. The
cooled mixture was poured into ice water at stirring.
The separated crystals were filtered off, washed with
distilled water, and recrystallized from methanol.
Yield of bisimides XVIII XXV 79 96%, their
characteristics are given in table.
Anhydride of cis-4-cyclohexene-1,2-dicarboxylic
acid was obtained as in [7], anhydride of trans-4,5-di-
bromocyclohexane-1,2-dicarboxylic along procedure
[8], anhydride of 1,4,5,6,7,7-hexachloro[2.2.1]hept-
5-ene-2,3-dicarboxylic acid was prepared by method
[9], anhydride of 1,2,3,4,11,11-hexachlorotricyclo-
[6.2.1.05,10]undec-2-ene-7,8-dicarboxylic acid by
method [10].
REFERENCES
1. Zhubanov, B.A., Arkhipova, I.V., and Almabe-
kov, O.A., Novye termostoikie geterotsiklicheskie
polimery (New Thermoresistal Polymers), Alma-Ata,
1979.
2. Salakhov, M.S., Musaeva, N.F., Karaeva, A.K.,
and Gasanova, A.A., Azerb. Khim. Zh., 1982, no. 5,
p. 55.
3. Nakanisi, K., Infrakrasnye spektry i stroenie organi-
cheskikh soedinenii (IR Sprctra and Organic Com-
pounds Structure), Moscow: Mir, 1965, 216 p.
Synthesis of cis-4-cyclohexene-1,2-dicarboxylic
acid monoamides VIII, IX. To a solution of 0.1 mol
of anhydride I in 20 ml of acetone was added at
vigorous stirring a solution of 0.1 mol of meta-(II) or
para-(IV) phenylenediamine in 100 ml of acetone.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 39 No. 2 2003