1
210
BAKIBAEV et al.
(method a) or 37% (method b). mp 192 194 C. IR
acetic acid within 17 h 3-acetoxy-3-phenyldihydroiso-
indolinone (V) was obtained that in boiling formic
acid within 5 h was transformed into compound IIIa
in 92% yield.
1
1
spectrum, , cm : 1670 (C=O). H NMR spectrum,
3
, ppm: 6.85 s (1H, C H), 7.07 8.10 m (14H,
H arom). 13C NMR spectrum, , ppm: 62.20 (C H),
3
1
21.73 145.78 (C arom), 170.74 (C=O). Found, %:
Thus we demonstrated that 2-carboxybenzo-
phenone (I) and its methyl ester IV cleanly reacted
with ureas IIa c in formic acid giving rise to
C 84.30; H 5.52; N 4.85. C H NO. Calculated, %:
C 84.19; H 5.30; N 4.91.
2
0
15
3
-phenylisoindolinones IIIa c which may serve as
(3-Oxo-1-phenyl-2,3-dihydro-1H-isoindol-1-yl)-
acetate (V). A mixture of 2.26 g (0.01 mol) of
2-carboxybenzophenone (I), 1.80 g (0.03 mol) of
urea IIa, and 60 ml of glacial acetic acid was
maintained for 17 h on a bath heated to 180 C. On
cooling the reaction mixture was diluted with 120 ml
of water, the separated precipitate was filtered off,
washed with warm water, and recrystallized from
alcohol. We obtained 1.65 g (62%) of compound V.
excellent synthons for preparation of new biologically
active compounds.
2
-R-3-phenylisoindolin-1-ones (IIIa c). General
procedure. A mixture of 0.01 mol of 2-carboxybenzo-
phenone (I) (method a) or 2-methoxycarbonylbenzo-
phenone (IV) (method b), 0.03 mol of urea IIa c,
and 60 ml of 99.8% formic acid was heated for 1 2 h
on a bath of temperature 120 C. Then within 1 h the
bath temperature was raised to 180 190 C, and at this
temperature the reaction mixture was maintained for
1
mp 245 246 C. H NMR spectrum, , ppm: 1.83
(
3H, CH ), 6.87 7.67 m (9H, H arom), 9.0 s (1H,
3
13
NH). C NMR spectrum,
7
1
, ppm: 20.91 (CH3),
2.43 (C ), 120.89 146.52 (C arom), 166.56(C=O),
68.20 (Me, C=O). Found, %: C 72.11; H 5.02;
2
0 41 h. On cooling the reaction mixture was diluted
1
with 120 ml of water, the separated precipitate was
filtered off, washed with warm water, and recrystal-
lized from alcohol.
N 5.35. C H NO . Calculated, %: 71.90; H 4.90;
1
6
13
3
N 5.24.
3
-Phenylisoindolin-1-one (IIIa). Reaction time
5 (method a) or 20 h (method b). Yield 86 (method
a) or 88% (method b). mp 218 219 C, IR spectrum,
The reaction progress was monitored and the homo-
geneity of compounds obtained was checked by TLC
on Silufol UV-254 plates, eluent benzene ethanol,
4: 1, spots visualized under UV irradiation. IR
spectra were recorded on spectrophotometer UR-20
from mulls in mineral oil. H and C NMR spectra
were registered on spectrometer Tesla BS 576A
2
1
1
,
cm : 1680 (C=O), 3215 br (NH). H NMR spec-
trum, , ppm: 5.88 d (1H, C H), 7.50 7.93 m (9H,
Harom), 8.94d (1H, NH). CNMR spectrum, , ppm:
3
1
3
1
13
3
5
9.63 (C H), 123.11 144.87 (C arom), 169.35
C=O). Found, %: C 80.55; H 5.48; N 6.47.
C H NO. Calculated, %: C 80.36; H 5.30; N 6.69.
(
(
operating frequencies 100 and 25.142 MHz re-
1
1
11
spectively) from solutions in DMSO-d6.
(
2
c) In 80 ml of boiling 99.8% formic acid was heated
.67 g (0.01 mol) of compound V for 17 h. Then on
REFERENCES
cooling the reaction mixture was diluted with 160 ml
of water, the separated precipitate was filtered off,
washed with warm water, and recrystallized from
alcohol. We obtained 1.92 g (92%) of compound IIIa.
Its characteristics are in full agreement with those of
the samples obtained by the previous procedures.
1. Vollmann, H.-J.W., Sredereck, K., and Brede-
reck, H.,Chem.,Ber., 1972, vol. 105, p. 2933.
2. Garonna, G. and Palazzo S.,Gazz. Chim. Ital., 1953,
vol. 83, p. 308.
3. Rose, R.E.,J. Am. Chem., 1991, vol. 33, p. 388.
4
. Salazkin, S.N., Fedoseenko, N.M.Yu Korshak, V.V.,
2
-Methyl-3-phenylisoindolin-1-one (IIIb). Reac-
tion time 32 (method a) or 27 h (method b). Yield
5 (method a) or 70% (method b). mp 97 98 C. IR
Vinogradov S.V.,Izv. Akad. Nauk SSSR, Ser. Khim.,
1
978, vol. 1, p. 137.
5
1
1
5. Bakibaev, A.A., Yagovkin, A.Yu., and Filimo-
nov, V.D., Zh. Org. Khim., 1991, vol. 7, p. 1512.
6. Bakibaev, A.A., Khim. Geterotsikl. Soed., 1995,
vol. 2, p. 1700.
spectrum, , cm : 1675 (C=O). H NMR spectrum,
3
,
ppm: 3.10 (3H, CH ), 5.86 s (1H, C H), 7.35
.03 m (9H, H arom). C NMR spectrum, , ppm:
5.51(NCH ), 66.05(C H), 127.53 142.58 (Carom),
77.50 (C=O). Found, %: C 80.80; H 6.01; N 6.19.
3
1
3
8
2
1
3
3
7
. Tietze, L.-F. and Eicher, T., Reactions and Syntheses
in the Organic Chemistry Laboratory, California:
University Science Books, 1989.
C H NO. Calculated, %: C 80.69; H 5.87; N 6.27.
1
4
13
2
,3-Diphenylisoindolin-1-one (IIIc). Reaction
8. Zotov, A.T., Mochevina (Urea), Moscow: Gos. Khim.
time 41 (method a) or 39 h (method b). Yield 28
Inst., 1963, p. 39.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 39 No. 8 2003