NAGIEV
302
2JАВ 9.6 Hz. Each component of the АВ system possesses
an additional fine structure originating from the spin-spin
oxane, N-methylpyrrolidone, acetone, mp 268–270°C. IR
spectrum, ν, cm–1: 3000–1440 (С–Н); 2950, 2885 (=СН);
2880, 2744 (=N–); 1750, 1710 (С=О); 1640, 820 (C=C);
1630, 1536 (С6Н4); 1380, 1210 (СОN); 1090 (O–H), 1005
coupling of the bridging protons with the protons Н1,4–6
.
In the downfield region (7.39 and 8.04 ppm) the spectrum
contains multiplet resonances corresponding to the five-
spin system АА1ВВ1С of aromatic protons.
1
(C–O), 680 (C–Cl). Н NMR spectrum, δ, ppm: 2.19 m
(1Н, HА), 2.50 m (1Н, HВ), 3.44 m (2H, H1,4), 6.45 m
(2H, H5,6), 7.39–8.04 m (4H, C6H4). Found, %: С 54.39;
Н 3.19; Cl 19.87; N 4.11. С16Н11Cl2NO4. Calculated, %:
С 54.55; Н 3.13; Cl 20.17; N 3.98.
The testing of the biological properties of imide IVc
showed that it exhibits herbicidal, fungicidal, bactericidal,
and biocidal action.
Compounds IVa, IVb were analogously prepared.
Dichloromaleic acid N-m-carboxyphenylimide
(IIIb). To a dispersion of 16.7 g (0.1 mol) of anhydride I
in 60 g of glacial acetic acid was added dropwise 13.7 g
(0.1 mol) of m-aminobenzoic acid. The mixture was
stirred for 30 min at 80°С and 90 min at 108°С. Then
the reaction mixture was cooled to 10°С, the precipi-
tate was filtered off, dried in a vacuum at 60°С. Yield
25.74 g (90%). Colorless crystals, well soluble in ben-
zene, toluene, acetone, chloroform. DMF, dioxane, mp
>250°С. IR spectrum, ν, cm–1: 1750–1705 (С=О), 1630,
985–900 (C=C), 1505, 1330–1305 (=N–), 1480–1400
(C–H), 1130–1120 (COH), 835–760 (C6H4), 690–650
(С–Cl). Found, %: С 46.44; Н 2.01; Cl 24.85; N 4.96.
С11Н5Cl2NO4. Calculated, %: С 46.15; Н 1.79; Cl 24.83;
N 4.90.
2,3-Dichlorobicyclo-[2.2.1]hept-5-ene-2,3-dicar-
boxylic acid N-o-carboxyphenylimide (IVa). Yield
83%, mp 223–225°С. IR spectrum, ν, cm–1: 3350,
2950–2800, 2765, 2735, 1740, 1710, 1600, 1500, 1300,
1
1230, 1090, 940, 800, 725, 675. Н NMR spectrum, δ,
ppm: 2.14 m (1H, HА), 2.46 m (1H, HВ), 3.45 m (2H,
H1,4), 6.46 m (2H, H5,6), 7.47–8.09 m (4H, C6H4). Found,
%: С 54.66; Н 2.98; Cl 20.56; N 3.92. C16H11Cl2NO4.
Calculated, %: С 54.55; Н 3.13; Cl 20.17; N 3.98.
2,3-Dichlorobicyclo-[2.2.1]hept-5-ene-2,3-dicar-
boxylic acid N-p-carboxyphenylimide (IVb). Yield
0.641 г (91%), mp 278–280°С. IR spectrum, ν, cm–1:
3300–3200, 2980–2800, 2770, 2740, 1750, 1710, 1605–
1
1505, 1475, 1370, 1320, 1120, 950, 880, 685. Н NMR
spectrum, δ, ppm: 2.17 m (1H, HА), 2.49 m (1H, HВ),
3.48 m (2H, H1,4), 6.48 m (2H, H5,6), 7.50–8.12 m (4H,
C6H4). Found, %: С 54.47; Н 3.02; Cl 20.56; N 3.76.
C16H11Cl2NO4. Calculated, %: С 54.55; Н 3.13; Cl 20.17;
N 3.98.
Compounds IIIa, IIIc were prepared similarly
Dichloromaleic acid N-o-carboxyphenylimide
(IIIа). Yield 80%, mp >240°С. IR spectrum, ν cm–1:
3260, 2700, 1750, 1505, 1480–1400, 1305–1300, 1130,
940, 780, 690, 650. Found, %: С 46.37; Н 1.99; Cl 24.89;
N 4.86. C11H5Cl2NO4. Calculated, %: С 46.15; Н 1.79;
Cl 24.83; N 4.90.
IR spectra were recorded on a spectrophotometer
Specord М-80 from pellets with KBr. 1Н NMR sperctra
were taken on a spectrometer Tesla ВS-484 (80 МHz) in
(СD3)2CO, internal reference TMS. Initial reagents and
solvents were prepared by procedures [2, 10].
Dichloromaleic acid N-p-carboxyphenylimide
(IIIc). Yield 26.6 g (93%), mp >250°С. IR spectrum, ν,
cm–1: 3260, 2800, 2650, 1750, 1705, 1605, 1480–1440,
1330–1305, 985, 835, 690, 670. Found, %: С 46.42;
Н 1.96; Cl 24.84; N 4.93. C11H5Cl2NO4. Calculated, %:
С 46.15; Н 1.79; Cl 24.83; N 4.90.
REFERENCES
1. Chinchilla, R., Farvello, R.L., Galindo, N., Najera, S.
2,3-Dichlorobicyclo-[2.2.1]hept-5-ene-2,3-di-
carboxylic acid N-p-carboxyphenylimide (IVc). To
a solution of 0.704 g (2 mmol) of imide IIIc in 10 ml
of benzene at 40°С was added dropwise within 15 min
a solution of 0.165 g (2.5 mmol) of freshly distilled
cyclopentadiene in 3 ml of benzene, the mixture was kept
for 4 h and evaporated on a water bath. The residue was
recrystallized from a mixture benzene–hexane, 1:1, dried
at 90°С. Yield 0.662 g (94%). Colorless powder, stable,
nonhygroscopic, nonexplosive, well soluble in DMF, di-
Tetrahedron: Asymmetry, 1999, vol. 10, p. 821.
2. Nagiev, Ya.M., Akhmedov, R.M., Bagirov, Sh.T., Farza-
liev, V.M., and Gasanov,A.I., Azerb. Khim. Zh., 2005, no.3,
p. 58.
3. Mamedbeili, (Mamedov), E.G., Kyazimova, T.G., Nag-
iev, Z.M., Abdiev, O.B., and Aliev, K.A., Zh. Org. Khim.,
2009, vol. 45, p. 81.
4. Nagiev, Ya.M., Shnulin, A.N., Akhmedov, R.M., Ba-
girov, Sh.T., and Nasibov, Sh.S., Abstracts of Papers,
Vsesoyuzn. soveshch. “Mekhanizmy reaktsii nukleofil’nogo
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 48 No. 2 2012