Cerium (IV) mediated oxidative dimerization of 3-oxoacid anilides and their cyclizations

Article abstract of DOI:10.1081/SCC-100000198

Investigation of the behavior of several anilides of 3-oxoacids in oxidation reaction with ceric ammonium nitrate has shown that selective intermolecular C-C bond formation, which led to their dimers, is typical of these compounds. These dimeric species were cyclized in two routes, A and B, leading to 3-[2′-(1′-aniline-3′-oxo)-indene]-quinoline-2-on derivatives with HCl_(g) (Route A), and with application of H₂SO₄ as a cyclization agent, gave furane-3,4-dicarboxylic acid derivatives (Route B).

Full text of DOI:10.1081/SCC-100000198

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CERIUM (IV) MEDIATED OXIDATIVE DIMERIZATION OF
3-OXOACID ANILIDES AND THEIR CYCLIZATIONS
B. Zaleska a & S. Lis a
a Department of Organic Chemistry , Jagiellonian University , Ingardena 3, Cracow, PL,
30-060, Poland
Published online: 16 Aug 2006.
To cite this article: B. Zaleska & S. Lis (2001) CERIUM (IV) MEDIATED OXIDATIVE DIMERIZATION OF 3-OXOACID ANILIDES AND
THEIR CYCLIZATIONS, Synthetic Communications: An International Journal for Rapid Communication of Synthetic Organic
Chemistry, 31:2, 189-197, DOI: 10.1081/SCC-100000198
To link to this article: http://dx.doi.org/10.1081/SCC-100000198
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SYNTHETIC COMMUNICATIONS, 31(2), 189–197 (2001)
CERIUM (IV) MEDIATED OXIDATIVE
DIMERIZATION OF 3-OXOACID ANILIDES
AND THEIR CYCLIZATIONS
B. Zaleska∗ and S. Lis
Department of Organic Chemistry, Jagiellonian University,
PL 30-060 Cracow, Ingardena 3, Poland
ABSTRACT
Investigation of the behavior of several anilides of 3-
oxoacids in oxidation reaction with ceric ammonium nitrate has
shown that selective intermolecular C-C bond formation, which
led to their dimers, is typical of these compounds. These dimeric
species were cyclized in two routes, A and B, leading to 3-[2ꢀ-
(1ꢀ-aniline-3ꢀ-oxo)-indene]-quinoline-2-on derivatives with HCl(g)
(Route A), and with application of H2SO4 as a cyclization agent,
gave furane-3,4-dicarboxylic acid derivatives (Route B).
For some years we have been employing anilides of 3-oxoacids as starting
material for the synthesis of several biologically active heterocyclic systems, such
as 1,4-thiazepine (1), pyridine (2), pyrrolidine (3), pyrrolo[2,3-c]pyridine (4), and
thiophene (5).
Although oxidative dimerization of 1,3-dicarbonyl compounds by ceric
ammonium nitrate (CAN) was investigated (5), there is only scant information
available on C-C bond forming reactions of 3-oxoacid derivatives (6).
∗ To whom correspondence should be addressed.
189
Copyright ꢁ 2001 by Marcel Dekker, Inc.
www.dekker.com
C

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==
==
==
==
==
==
==
==
==
==
a - R Me, X H, Y H; b - R Me, X H, Y Cl; c - R Ph, X H, Y H; d -R p-CH3-
== == == == == == == == == ==
C6H4, X H, Y H; e - R Ph, X H, Y Me; f - R Ph, X H,Y OMe; g - R Ph, X H,
==
==
==
==
==
==
==
==
==
==
Y Cl; h - R Ph, X H, Y NO2; i - R Ph, X Me,Y H; j - R Ph, X Et, Y H
Scheme 1.
We have initiated studies in this area and our preliminary results on CAN
mediated dimerization of various anilides of 3-oxoacids and further cyclisation of
dimeric species are reported here.
We have found that treatment of 3-oxoacid anilides 1 with 2 mol equiv.
of CAN in methanol gave excellent isolated yields of the dimeric product 2
(Scheme 1). A different course was observed only for N-methylanilide of ben-
zoylacetic acid 1i, where oxidative cyclization product, N-methyl isatine 3i was
formed. Whereas, in the case of p-nitroanilide of benzoylacetic acid 1h in this
oxidation process, mono p-nitroanilide of oxalyl acid was isolated.
This CAN mediated C-C bond forming reaction leading to compounds 2
proceeded with a change of color from light yellow to deep orange, which indi-
cated complexation with metal. Based on an already proposed mechanism (7,8),
change of color suggests that dimers 2 formation is of radical type that occurs
after the complexation of ceric (IV) ion with 1,3-dicarbonyl system of 3-oxoacid
anilides.
The structure of the dimerization products 2, as a mixture of meso and d,1
pair of 2,3-dibenzoylsuccinic acid anilides, is clear from their spectral data.
The 13C nmr spectra of compounds 2 confirmed the presence of C2-C3 bond
of succinic acid anilide 2, because the diagnostic signal at 60.4 ppm of 2a corre-
sponds to sp3 hybridized carbon atoms. This signal assignment was supported by
1H nmr spectra of compound 2a, which show in the place of the two characteristic
signals for anilide 1a at 3.55 ppm and 4.95 ppm (tautomeric equilibrium) one
at 4.64 ppm (2 × CH). Additionally, this fact was confirmed by DEPT 135 and
HETCOR nmr spectra of compound 2a. Electron impact (MS/EI) spectra of 2 dis-
play diagnostic peaks m/z of M+ ions, which indicates dimerization of 3-oxoacid
anilides 1.

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191
Scheme 2.
Intramolecular Cyclization of Compounds 2 to Quinoline
Derivatives 4 (Route A)
The saturation of an ethanolic suspension of the anilides of 2,3-disubstituted
succinic acid 2 with HCl(g) at 50◦C (3 h) gave, almost quantitatively, new quinoline
derivatives 4 (Scheme 2). During this intramolecular cyclization of compounds 2,
one fragment gave a quinoline ring system, but the other formed the indene-2-on
(9), present as the substituent at position 3 of the quinoline-2-on.
The structure of obtained new compounds 4 was elucidated on the basis of
their spectroscopic data. The ir spectrum showed two intensive absorption peaks
of carbonyl groups at 1749 cm−1 attributed to indene system and at 1680 cm−1 of
quinoline-2-on.
The analysis of 13C nmr data of compound 4c clearly indicates the presence
of two different carbons of carbonyl group at 169 ppm of C-2 quinoline ring and
at 187 ppm of indene-2-on.
The MS spectra of 4c show peaks assigned to M+ ion as well as 1/2 M+ (A)
ion. Characteristic fragmentation of quinoline-4-on system confirmed the presence
of ions B, present in all spectra of compound 4, formed due to the α and β cleavages
of the heterocyclic ring (Figure 1). Indene-2-on fragmentation give ions D.
Figure 1.

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ZALESKA AND LIS
Intramolecular Cyclization of Compounds 2 to Furan
Derivatives 5 (Route B)
Other type of cyclization process of dimers 2 took place, when conc. H2SO4
was used as cyclization agent (Scheme 2). In this case intramolecular ring closure
led to 3,4-dicarboxylic acid of 2,5-diphenyl-furane 5. Analysis of the ir, nmr as
well as ms (10) spectra confirmed proposed structure of furan derivatives 5.
Cyclization of 3-Oxoacid Thioanilides to 1,2,4-Dithiazol 7 and
Isothiazol 8 Derivatives
Our experience with the CAN promoted C-C bond formation described
above prompted us to test the possibility of exploiting this procedure to prepare
heterocyclic compounds starting from 3-oxoacid tioanilide 6. Oxygenation of ben-
zoylthioacetic acid anilide 6 with CAN led to 1,2,4-ditiazol derivatives 7 (11), by
intermolecular S-S bond formation. This cyclization to heterocyclic system 7 took
place with elimination of one molecule of aniline (Scheme 3).
Usage of 3-aminothiocinnamic acid anilides 8 allows formation of isothiazol
derivatives 9 (11) by N-S intermolecular bond formation.
Although the chemistry of 1,2,4-dithiazol 7 as well as isothiazol 9 is well
researched (11), this method of their preparation is novel.
In conclusion, oxidation of 3-oxoacid anilides promoted by ceric ammo-
nium nitrate leads to intermolecular C2-C2 bond formation, typical to 1,3-
dioxocompounds. Dimeric species 2 are valuable intermediates for synthesis of
new, pharmacologically interesting, heterocyclic derivatives such as quinoline 4,
substituted in position 3 with indene, and furan 3,4-dicarboxylic acid derivatives
5, known as drugs (12).
Scheme 3.

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3-OXOACID ANILIDES
193
All the methods of synthesis described here are very efficient, and can be ap-
plied conveniently for the preparation of new compounds 4 and 5 as well as 7 and 8.
EXPERIMENTAL
General Procedure for the Preparation of 2,3-Disubstituted
Succinic Acid Anilide 2
A solution of CAN (2 mmol) in methanol (10 mL) was added dropwise to an
ice-cold solution of 3-oxoacid anilide 1 (1 mmol) in methanol (10 mL) and stirred
for 3 h. The reaction mixture was left for 12 h, and after this time it was diluted with
water (100 mL), and extracted with CH2Cl2 (3 × 20 mL). The colorless precipitate
was filtered off and washed with water.
2a. Yield 60%; m.p. 231–232◦C; C20H20N2O4 · H2O, MW = 370 a.u., CHN
requires: C-64.86%, H-5.94%, N-7.57%; found: C-64.66%, H-5.29%, N-7.60%;
ir (KBr, cm−1): 1651, 1680 (νC==O), 3052 (νC-H), 3251 (νN-H); 1H nmr (DMSO-
d6, ppm) 2.24 (s, 6H, CH3-), 4.64 (s, 2H, CH), 7.02–7.58 (m, 10H, C(Ar)), 10.72
(s, 2H, NH); 13C nmr (DMSO-d6, ppm) 29.22 (CH3), 60.37 (-CH-), 119.46,
==
123.90, 128.95, 138.67 (C(Ar)), 164.84, 201.93 (C O); MS-EI (70 eV, m/e): 352
(8.15%), 334 (19.24%), 309 (30.66%), 292 (3.35%), 259 (9.59%), 241 (24.46%),
216 (53.73%) 173 (47.12%), 93 (100%), 77 (22.11%).
2b. Yield 58%; m.p. 198◦–199◦C; C20H18N2O4Cl2 · H2O, MW = 421 a.u.;
CHN requires: C-57.0%, H-4.3%, N-6.6% ; found: C-57.2%, H-4.0%, N-6.9%;
ir (KBr, cm−1): 1648, 1683 (νC==O), 3058 (νC-H), 3268 (νN-H); 1H nmr (DMSO-
d6, ppm) 2.28 (s, 6H, CH3-), 4.64 (s, 2H, CH), 7.34–7.57 (m, 8H, C(Ar)), 10.88
(s, 2H, NH); 13C nmr (DMSO-d6, ppm) 29.00 (CH3), 60.52 (-CH-), 120.81;
==
127.55; 128.79; 137.39 (C(Ar)), 164.75; 201.31 (C O).
2c. Yield 84%; m.p. 247◦–248◦C; C30H24N2O4 · H2O, MW = 494 a.u.,
CHN requires: C-72.9%, H-5.3%, N-5.7%; found: C-73.13%, H-5.37%, N-5.61%;
1
ir (KBr, cm−1): 1661, 1686 (νC==O), 3062, 3132 (νC-H), 3243, 3330 (νN-H); H
nmr (DMSO-d6, ppm): 5.60 (s, 2H, CH), 6.98–8.22 (m, 20H, C(Ar)), 10.64,
10.86 (2 × s, 2H, NH); 13C nmr (DMSO-d6, ppm): 55.45 (-CH-), 119.35, 124.05,
==
128.63, 128.76, 129.00, 133.95, 135.44, 138.16 (C(Ar)), 165.33, 193.42 (C O),
MS-EI (70 eV, m/e): 476 (1.26%), 458 (4.54%), 348 (8.57%), 371 (23.34%), 365
(10.04%), 291 (11.09%), 278 (23.39%), 265 (9.89%), 119 (6.80%), 105 (100%),
93 (40.97%), 77 (35.09%).
2d. Yield 75%; m.p. 248◦–249◦C; C32H28N2O4 · H2O, MW = 522 a.u.,
CHN requires: C-73.5%, H-5.8%, N-5.4%; found: C-74.06%, H-5.22%, N-5.17%;
1
ir (KBr, cm−1): 1643, 1693 (νC==O), 3049, 3124 (νC-H), 3243 (νN-H); H nmr
(DMSO-d6, ppm): 2.16 (s, 6H, CH3), 5.58 (s, 2H, CH), 6.87–8.96 (m, 18H, C(Ar)),
10.50, 10.76 (2 × s, 2H, NH); 13C nmr (DMSO-d6, ppm): 20.63 (CH3), 56.71

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ZALESKA AND LIS
(-CH-), 120.04, 128.69, 129.20, 129.26, 133.34, 134.13, 135.76, 135.98 (C(Ar)),
==
165.36, 193.75 (C O); MS-EI (70 eV, m/e): 504 (2.25%), 486 (11.50%), 468
(6.49%), 399 (30.93%), 397 (12.52%), 379 (68.22%), 353 (14.89%), 333 (13.15%)
293 (2.59%) 292 (15.83%), 266 (11.58%), 133 (12.77%), 107 (100%), 105
(24.39%).
2e. Yield 89%; m.p. 244◦–245◦C; C32H28N2O4 · H2O, MW = 522 a.u., CHN
requires: C-69.31%, H-5.42%, N-5.05%; found: C-69.27%, H-5.18%, N-5.33%;
ir (KBr, cm−1): 1649, 1680 (νC==O), 2916, 2973, 3036, 3130 (νC-H), 3256, 3337
1
(νN-H); H nmr (DMSO-d6, ppm): 2.37 (s, 6H, CH3), 5.54 (s, 2H, CH), 6.96–
8.13 (m, 18H, C(Ar)), 10.82 (s, 2H, NH); 13C nmr (DMSO-d6, ppm): 21.07
(CH3), 56.28 (-CH-), 119.62, 123.63, 126.03, 126.79, 128.54, 129.22, 137.40,
==
144.39 (C(Ar)), 165.41, 192.77 (C O); MS-EI (70 eV, m/e): 504 (1.18%), 486
(3.14%), 412 (6.49%), 385 (12.03%), 319 (9.66%), 293 (12.40%), 266 (14.76%),
119 (100%), 93 (23.49%).
2f. Yield 68%; m.p. 246◦–247◦C; C32H28N2O6 · H2O, MW = 554 a.u., CHN
requires: C-69.31%, H-5.42%, N-5.05%; found: C-69.04%, H-5.30%, N-5.21%;
ir (KBr, cm−1): 1649, 1687 (νC==O), 2835, 2961, 3055, 3130 (νC-H), 3243 (νN-H);
1H nmr (DMSO-d6, ppm): 3.65 (s, 6H, CH3), 5.54 (s, 2H, CH), 6.76–8.22 (m,
18H, C(Ar)), 10.70 (s, 2H, NH); 13C nmr (DMSO-d6, ppm) 55.8 (CH3), 56.28
(-CH-), 113.75, 121.23, 128.35, 128.88, 131.26, 133.80, 135.44, 155.68 (C(Ar)),
==
164.81, 193,46 (C O).
2g. Yield 87%; m.p. 244◦–245◦C; C30H20N2O4Cl2 · H2O, MW = 561 a.u.,
CHN requires: C-64.17%, H-3.92%, N-4.99%; found: C-64.26%, H-3.67%, N-
5.14%; ir (KBr, cm−1): 1649, 1687 (νC==O), 3049, 3117 (νC-H), 3237, 3318 (νN-H);
1H nmr (DMSO-d6, ppm): 5.56 (s, 2H, CH), 7.23–8.19 (m, 18H, C(Ar)), 10.99
(s, 2H, NH); 13C nmr (DMSO-d6, ppm): 56.79 (-CH-), 121.49, 128.17, 128.79,
==
129.04, 129.49, 134.49, 135.76, 137.43 (C(Ar)), 165.93, 193.55 (C O); MS-EI
(70 eV, m/e): 546 (2.19%), 544 (3.84%), 528 (4.63%), 526 (6.96%), 441 (24.85%),
439 (37.54%), 418 (20.22%), 312 (26.93%), 286 (36.19%), 265 (25.05%), 155
(9.49%), 153 (33.20%), 129 (28.29%), 127 (93.08%), 105 (100%).
2j. Yield 92%; m.p. 195◦–196%◦C; C34H32N2O4, MW = 532 a.u.; CHN re-
quires: C-76.7%, H-6.1%, N-5.3%; found: C-76.18%, H-5.88%, N-5.13%;
1
ir (KBr, cm−1): 1636, 1680 (νC==O), 2973, 3061 (νC-H), 3431 (νN-H); H nmr
(CDCl3, ppm): 0.69 (t, 3H, CH3), 1.16 (t, 3H, CH3), 3.12 (m, 1H, CH2), 3.65
(m, 2H, CH2), 3.90 (m, 1H, CH2), 5.46 (s, 1H, CH), 5.58 (s, 1H, CH), 6.40–7.55
(m, 20H, C(Ar)); 13C nmr (CDCl3, ppm): 12.34, 12.83 (CH3), 45.01, 45.05 (CH),
53.16, 53.53 (CH2), 127.65, 127.96, 128.10, 129.02, 129.14, 129.58, 132.70,
==
132.73, 136.07, 136.92, 140.84, 141.11 (C(Ar)), 165.67, 167.07 (C O), 196.33,
==
196.84 (C O); MS-EI (70 eV, m/e): 532 (1.16%), 514 (1.39%), 427 (33.59%), 412
(100%), 306 (36.31%), 291 (31.65%), 148 (46.67%), 120 (6.42%), 105 (26.86%).

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195
Procedure for Preparation
of 3-[2ꢀ-(1ꢀ-Aniline-3ꢀ-oxo)-indene]-4-phenyl-2-oxo-quinoline
4c (Route A)
A suspension of apropriate compound 2 (3 mmol) in 10 mL of methanol was
stirred at 50◦C and saturated with HCl(g) (3 h). Red crystalline compound 4c was
filtered off.
4c. Yield 65%; m.p. > 300◦C; C30H20N2O2 · HCl, MW = 440 a.u.; CHN
requires: C-75.51%, H-4.20%, N-5.88%, found: C-75.18%, H-4.88%, N-5.67%;
ir (KBr, cm−1): 1680, 1749 (νC==O), 3397 (νN-H); 1H nmr (D2SO4, ppm): 7.02–
13
==
8.15 (m, 18H, C(Ar)); C nmr (D2SO4, ppm): 125.86 ( C-); 127.44, 132.10,
132.65, 133.54, 133.79, 134.89, 140.35, 140.73, 147.87 (C(Ar)), 148.49 (C-NH),
==
169.18, 187.02 (C O); MS-EI (70 eV, m/e): 440 (100%), 413 (11.81%, B), 364
(12.75%), 348 (5.3%), 220 (3.60%), 180 (30.50%), 105 (7.07%).
4d. Yield 70%; m.p. > 300◦C; C32H24N2O2 · HCl, MW = 468 a.u.; CHN
requires: C-76.19%, H-4.96%, N-5.56%, found: C-76.08%, H-4.75%, N-5.71%;
1
ir (KBr, cm−1): 1680, 1762 (νC==O), 3419 (νN-H); H nmr (D2SO4, ppm): 2.46
(s, 3H, CH3), 3.17 (s, 3H, CH3), 7.03–8.11 (m, 16H, C(Ar)); 13C nmr (D2SO4,
==
ppm): 23.15, 37.48 (CH3), 125.86 ( C-); 127.44, 132.11, 132.45, 133.64, 133.39,
==
134.59, 140.45, 140.73, 147.87 (C(Ar)), 148.60 (C-NH), 169.60, 187.96 (C O);
MS-EI (70 eV, m/e): 468 (100%), 454 (7.32%), 440 (1.81%), 379 (22.07%), 361
(1.3%), 234 (3.84%), 194 (25.73%), 105 (7.07%).
4e. Yield 82%; m.p. > 300◦C; C32H24N2O2 · HCl, MW = 468 a.u.; CHN
requires: C-76.19%, H-4.96%, N-5.56%, found: C-76.27%, H-4.83%, N-5.42%;
1
ir (KBr, cm−1): 1662, 1680, (νC==O), 3437 (νN-H); H nmr (D2SO4, ppm): 2.56
(s, 3H, CH3), 3.16 (s, 3H, CH3), 7.33–7.88 (m, 16H, C(Ar)); 13C nmr (D2SO4,
==
ppm): 25.81, 37.48 (CH3), 123.41 ( C-), 127.44, 132.11, 132.45, 134.50, 135.01,
==
135.20, 136.03, 140.73, 141.24 (C(Ar)), 166.30 (C-NH), 170.00, 184.62 (C O);
MS-EI (70 eV, m/e): 468 (100%), 440 (1.62%), 376 (1.32%), 234 (1.42%), 194
(19.95%), 119 (3.94%).
4f. Yield 63%; m.p. >300◦C; C32H24N2O4 · HCl, MW = 500 a.u.; CHN
requires: C-71.64%, H-4.66%, N-5.22%, found: C-71.53%, H-4.33%, N-5.57%;
ir (KBr, cm−1): 1680, 1721 (νC==O), 2835, 2961, 3017 (νC-H), 3431 (νN-H).
4g. Yield 78%; m.p. > 300◦C; C30H18N2O2Cl2 · HCl, MW = 509 a.u.; CHN
requires: C-66.06%, H-3.49%, N-5.14%, found: C-66.43%, H-3.71%, N-5.01%;
1
ir (KBr, cm−1): 1660, 1687 (νC==O), 3049, 3092 (νC-H), 3450 (νN-H); H nmr
(D2SO4, ppm):6.73–7.68(m, 16H, C(Ar));13Cnmr(D2SO4, ppm):125.65 ( C-),
==
129.46, 131.16, 131.94, 132.83, 133.09, 134.07, 134.21, 134.51, 140.58, 142.98
==
(C(Ar)), 149.14 (C-NH), 168.61, 187.36 (C O), MS-EI (70 eV, m/e): 510 (100%),
398 (1.75%), 216 (30.50%), 129 (7.25%).

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Procedure for Preparation of Dianilides
of 2,5-Diphenyl-furane-3,4-dicarboxylic
Acid 5 (Route B)
A mixture of (3 mmol) of compound 2 and 5 mL of conc. H2SO4 in 10 mL
of ethanol was stirred for 1 h at room temp. After 1 h, 10 mL of water was added.
Crystallinecompound5was filteredoff. TheproductwaspurifiedbyAl2O3 column
(CHCl3), giving colorless compound 5.
5c. Yield 92%; m.p. 219◦–220◦C; C30H22N2O3, MW = 458 a.u.; CHN
requires: C-78.60%, H-4.80%, N-6.11%, found: C-78.46%, H-4.74%, N-6.21%;
ir (KBr, cm−1): 1624 (νC==O), 3080 (νC-H), 3205, 3318 (νN-H); 1H nmr (CDCl3,
ppm): 7.05–8.72 (m, 20H, C(Ar)), 10.32 (s, 2H, NH); 13C nmr (CDCl3, ppm):
==
117.93 (C C), 119.62, 124.42, 124.98, 127.22, 127.80, 128.60, 129.51, 133.51
==
==
(C(Ar)), 137.62 (O-C C), 162.10 (C O); MS-EI (70 eV, m/e): 458 (26.23%),
366 (100%), 247 (1.85%), 105 (22.81%).
5d. Yield 95%; m.p. 214◦–215◦C; C32H26N2O3, MW = 486 a.u.; CHN
requires: C-79.01%, H-5.35%, N-5.76%, found: C-78.94%, H-5.21%, N-5.71%;
ir (KBr, cm−1): 1647 (νC==O), 2863, 3052 (νC-H), 3188, 3240 (νN-H); H nmr
1
(CDCl3, ppm): 2.32 (s, 6H, CH3), 6.89–7.93 (m, 18H, C(Ar)), 8.93 (s, 2H, NH);
==
C nmr (CDCl3, ppm): 20.91 (CH3), 117.98 (C C), 119.23, 120.43, 125.82,
13
==
==
127.58, 128.33, 128.91, 129.51, 134.53 (C(Ar)), 153.49 (O-C C), 162.07 (C O).
5j. Yield 94%; m.p. 186◦–187◦C; C34H30N2O3, MW = 514 a.u.; CHN re-
quires: C-79.38%, H-5.84%, N-5.45%, found: C-79.45%, H-5.58%, N-5.62%;
ir (KBr, cm−1): 1667 (νC==O), 2878, 3082 (νC-H); H nmr (CDCl3, ppm): 1.11,
1
1.29 (t, 6H, CH3), 3.88, 4.29 (q, 4H, CH2), 6.42–7.72 (m, 20H, C(Ar)), 13C nmr
==
(CDCl3, ppm): 12.78, 14.10 (CH3), 44.06, 44.59 (CH2), 107.38 (C C), 119.75,
==
120.02, 125.83, 127.35, 128.18, 128.70, 129.31, 144.75 (C(Ar)), 155.97 (O-C C),
==
162.73 (C O), MS-EI (70 eV, m/e): 514 (17.20%), 394 (54.93%), 367 (27.14%),
317 (100%), 247 (58.14%), 105 (85.22%).
REFERENCES
1. Zaleska, B.; Ciez˙, D.; Grochowski, J.; Serda, P.; Winnik, W. Lieb. Ann. Chem.
1995, 12, 196.
´
2. Zaleska, B.; Slusarska, B. Monatsh. Chem. 1981, 112, 1187–1194.
˙
3. Zankowska-Jasin´ska, W.; Zaleska, B.; Walocha, K. Zesz. Nauk. Univ. Jagiell.
Prace Chem. 1973, 18, 137.
4. Zaleska, B. J. Pract. Chem. 1987, 329 (5), 787.
5. Cho, L.Y.; Romero, J.R. Tetrahedr. Lett. 1995, 36 (48), 8757–8760.
6. Dong, J.H.; Qiu, K.Y.; Feng, X.D. Macromol. Chem. Phys. 1994, 195,
823–831.

ORDER
REPRINTS
3-OXOACID ANILIDES
197
7. Ho, T.L. Organic Synthesis by Oxidation with Metal Compounds, Mijs, W.J.;
de Jonge, C.R.H.I.; Eds.; Plenum Press: New York, 1986; 569–631.
8. Bacciocchi, E.; Ruzziconi, R. Free Radicals in Synthesis and Biology,
Minisci, F., Ed.; Series C: Mathematical and Physical Sciences; Kluwer
Academic Publisher: Amsterdam, 1988, 260, 155–185.
9. Hursthouse, M.B.; Karaulov, A.I.; Ciechanowicz-Rutkowska, M.; Kolasa,
˙
A.; Zankowska-Jasin´ska, W. Acta Cryst. 1992, C48, 1257–1260.
10. Karminski-Zamola, G.; Fisˇer-Jakic´, L. Rapid Comm. Mass Spectr. 1995, 9,
781–782.
11. Zaleska, B.; Ciez, D.; Haas, A. Synth. Commun. 1996, 26, 4165–4172.
12. Takeda, M.; Yamazaki, J.; Kikawa, M. Jpn. Kokai Tokkyo Koho Jp. 09 12,457
[97 12,457] (Cl. A61K31/34) Jan. 14, 1997.
Accepted April 11, 2000

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