Polycyclic heteroaromatics from reactions of acylbenzotriazoles with aryl isocyanates

Article abstract of DOI:10.1021/jo0009604

N-Acylbenzotriazoles react with aryl isocyanates to form, depending on the type of acyl group, compounds based on five different classes of polycyclic heteroaromatics. Higher alkanoyl-, acetyl-, acetoacetyl-, aroyl-, and cinnamoylbenzotriazoles yield, respectively, derivatives of quinoline, pyrimidino[5,4-c]quinoline, benzo[b]-1,8-naphthyridine, phenanthridine, and indolo[2,3-b]quinoline by incorporating 3, 3, 4, 2, and 2 molecules, respectively, of the isocyanate per acylbenzotriazole molecule.

Full text of DOI:10.1021/jo0009604

J . Org. Chem. 2000, 65, 8069-8073
8069
P olycyclic Heter oa r om a tics fr om Rea ction s of Acylben zotr ia zoles
w ith Ar yl Isocya n a tes
Alan R. Katritzky,* Tian-Bao Huang, and Michael V. Voronkov
Department of Chemistry, Center for Heterocyclic Compounds, University of Florida,
Gainesville, Florida 32611-7200
Peter J . Steel*
Department of Chemistry, University of Canterbury, Christchurch, New Zealand
katritzky@chem.ufl.edu
Received J une 26, 2000
N-Acylbenzotriazoles react with aryl isocyanates to form, depending on the type of acyl group,
compounds based on five different classes of polycyclic heteroaromatics. Higher alkanoyl-, acetyl-,
acetoacetyl-, aroyl-, and cinnamoylbenzotriazoles yield, respectively, derivatives of quinoline,
pyrimidino[5,4-c]quinoline, benzo[b]-1,8-naphthyridine, phenanthridine, and indolo[2,3-b]quinoline
by incorporating 3, 3, 4, 2, and 2 molecules, respectively, of the isocyanate per acylbenzotriazole
molecule.
Sch em e 1
In tr od u ction
Aryl isocyanates have been widely used for preparation
of various heterocyclic compounds.1a-g Condensation of
aryl isocyanates with aldehydes has provided short and
efficient entries to diverse heterocycles.2a,b Previously
reported condensations of isocyanates with carboxylic
acid derivatives have afforded triazines,3 triazoles,4
pyrimidones,5a,b pyridones,6 and some other heterocy-
cles.6,7a,b We now report condensations of aryl isocyanates
with five distinct types of N-acylbenzotriazoles to provide
synthetic approaches to quinolines, pyrimidino[5,4-c]-
quinolines, benz[b]-1,8-naphthyridine, phenanthridines,
and indolo[2,3-b]quinolines and compare our results with
those previously reported.
Resu lts a n d Discu ssion
Qu in olin e Syn th esis. 1-Alkanoylbenzotriazoles 1a ,b
(1 equiv) heated neat in the presence of an aryl isocyanate
(3 equiv) in a sealed tube for 24 h gave quinolines 2a
and 2b in 86 and 83% yields, respectively (Scheme 1).
The structure of 2a was confirmed by X-ray crystal-
lography (Figure S1), and that of 2b1b was assigned by
analogy and by spectroscopic data comparisons. In the
X-ray structure of 2a , the ring of the C2-anilino substitu-
ent is approximately coplanar with the quinoline ring,
whereas the C4 substituent is approximately orthogonal
to it. The nature of substituents R1 and R2 did not
significantly influence the yields of such quinolines,
except 1-benzotriazolyl-1-carbonyl-3-chloropropane (1c,
R1 ) CH2CH2Cl) on heating with tolyl isocyanate gave
N-phenyl-2-pyrrolidone and no quinoline product.8 Quin-
olines of type 2 were previously prepared by heating
aniline and diethyl malonate9a or N-acetylanthranilates9b
in hexamethylphosphoric triamide (HMPT) but only in
(1) (a) Sheehan, J . C.; Daves, G. D., J r. J . Org. Chem. 1965, 30, 3247.
(b) Merault, G.; Bourgeois, P.; Duffaut, N. Bull. Soc. Chim. Fr. 1974,
1949. (c) Ohtsuka, Y. J . Org. Chem. 1978, 43, 3231. (d) Shindo, H.;
Fujishita, T.; Sasatani, T.; Chomei, N.; Takada, S. Heterocycles 1989,
29, 899. (e) Palacios, F.; Aparicio, D.; Garcia, J . Tetrahedron 1997, 53,
2931. (f) Molina, P.; Alcantara, J .; Lopez-Leonardo, C. Tetrahedron
1997, 53, 3281. (g) Shi, C.; Zhang, Q.; Wang, K. K. J . Org. Chem. 1999,
64, 925.
(2) (a) Minami, T.; Ohshiro, Y.; Agawa, T. J . Org. Chem. 1974, 39,
3516. (b) Yamamoto, I.; Furukawa, T.; Nakajima, H.; Gotoh, H. J .
Chem. Soc., Perkin Trans. 1 1976, 1597.
(3) Argabright, P. A.; Phillips, B. L. J . Heterocycl. Chem. 1970, 7,
725.
(4) Bruche, L.; Garanti, L.; Zecchi, G. J . Chem. Soc., Perkin Trans.
1 1986, 2177.
(5) (a) Behrend, R.; Meyer, F. C.; Buchholz, Y. Liebigs Ann. Chem.
1901, 314, 200. (b) Capuano, L.; Boschat, P.; Heyer, H. W.; Wachter,
G. Chem. Ber. 1973, 106, 312.
(6) Ozaki, S.; Nagase, T.; Kato, T. Heterocycles 1988, 27, 2063.
(7) (a) Huisgen, R.; Grashey, R.; Knupfer, H.; Kunz, R.; Seidel, M.
Chem. Ber. 1964, 97, 1085. (b) Capuano, L.; Bronder, M.; Djokar, K.;
Muller, I. Chem. Ber. 1980, 113, 395.
(8) Toth, G.; Kovacs, A.; Bitter, I.; Duddeck, H. Liebigs Ann. Chem
1991, 1215.
(9) (a) Pedersen, E. B. Acta Chem. Scand. 1976, B30, 133. (b)
Pedersen, E. B. Tetrahedron 1977, 33, 217.
10.1021/jo0009604 CCC: $19.00 © 2000 American Chemical Society
Published on Web 10/21/2000

8070 J . Org. Chem., Vol. 65, No. 23, 2000
Katritzky et al.
Sch em e 2
5% yield for R1 ) alkyl. For R1 ) H the yield of 2 was
17-70% depending on the nature of R2.
reacting them with carbonyl compounds,2a,b enamines,1e
imines,15 and other compounds.1b,16 However, reactions
1 f 2 offer a higher degree of functionalization as well
as mechanistic diversity.
Although it is known that some benzotriazole deriva-
tives extrude nitrogen to form quinolines,10a-e structures
2a and 2b clearly excluded the possibility of the quinoline
ring arising from the benzotriazole moiety. The mecha-
nism of the conversion 1 f 2 likely involves the ketene
derived from the 1-acylbenzotriazole11 reacting with the
carbodiimide12 4 formed from two molecules of the
isocyanate. The resulting 4-quinolone 3 apparently reacts
further with another molecule of isocyanate to yield the
observed product 2.13 These intermediates are different
to the imine or enamine species which were suggested
earlier as intermediates in condensations of aldehydes
with isocyanates.2a,b Our mechanistic speculations are
supported by the facts that (1) the corresponding 1-ben-
zotriazolyl imines14a,b failed to produce quinolines under
these reaction conditions and (2) the reaction of N,N′-
bis(4-methylphenyl)carbodiimide with 1-butyrylbenzo-
triazole (1a ) afforded 3-ethyl-7-methyl-N2-(4-methyl-1,4-
cyclohexadien-1-yl)-N4-(4-methylphenyl)-2,4-quinolinedi-
amine (2c) in 76% yield (Scheme 1).
P yr im idin o[4,5-b]qu in olin es. We found that 1-acetyl-
benzotriazole 1c, when heated with an excess of C6H5-
NCO or p-MeC6H4NCO in a sealed tube at 210 °C for 24
h, gave pyrimidino[5,4-c]quinolines 5a and 5b in 66% and
86% yields, respectively (Scheme 2). The structures of
compounds 5a and 5b were determined by X-ray crystal-
lography (Figure S2). The structures and conformations
of these two molecules are very similar, and in each case,
the NH hydrogen of the anilino substituent is involved
in an intramolecular hydrogen bond to the nearby car-
bonyl oxygen. We believe that mechanistically the first
steps in this reaction are very similar to the transforma-
tion 1 f 2 discussed above and probably give 3. The
reaction then proceeds via the formation of 2d followed
by reaction with two more moles of ArNCO. The 3-posi-
tion in 2d is somewhat nucleophilic and forms another
pyrimidine ring under the reaction conditions. The GC/
MS of the reaction mixture indicates the presence of
molecular ions for 5a and 5b.
Previously, compounds of type 5 were available via
Wittig reaction of isocyanates with phosphorus ylides
derived from bromoacetic esters.7b This earlier method
gave 5 mixed with other products: our direct condensa-
tion of isocyanates with 1-acetylbenzotriazole 1c affords
the pyrimidino[5,4-c]quinolines 5a as a 6:1 mixture with
6 and 5b as the only product in 66% and 68% yields.
Curiously enough under identical conditions 1h displayed
just the opposite selectivity yielding 6 as the only product.
This quite remarkable difference between chemical be-
havior of benzotriazolyl and 5,6-dimethylbenzotriazolyl
moieties suggests more complex mechanism and their
intimate involvement in it.
Reactions 1 f 2 are somewhat similar to the direct
syntheses of quinoline systems from aryl isocyanates by
(10) (a) Kulagowski, J . J .; Moody, C. J .; Rees, C. W. J . Chem. Soc.,
Perkin Trans. 1 1985, 2725. (b) Barker, S. J .; J ones, G. B.; Randles,
K. R.; Storr, R. C. Tetrahedron Lett. 1988, 29, 953. (c) Katritzky, A.
R.; Lan, X.; Lam, J . N. Chem. Ber. 1991, 124, 1431. (d) Katritzky, A.
R.; Yang, B. J . Heterocycl. Chem. 1996, 33, 607. (e) Katritzky, A. R.;
Du, W.; Matsukawa, Y.; Ghiviriga, I.; Denisenko, S. N. J . Heterocycl.
Chem. 1999, 36, 927.
(11) Katritzky, A. R.; Soleiman M.; Yang, B. Heteroatom Chem.
1996, 7, 367.
(12) The formation of carbodiimide was suggested by the side
products isolatedsthe corresponding amides and a carbodiimide dimer.
Previous publications report reaction of carbodiimide with aryl isocy-
anate to form 2-imino-1,3-diazetan-4-ones: (a) Ulrich, H.; Richter, R.;
Tucker, B. J . Heterocyclic Chem. 1987, 24, 1121. (b) Farrissey, W. J .,
J r.; Ricciardi, R. J .; Sayigh, A. A. R. J . Org. Chem. 1968, 33, 1913. (c)
Neidlein, R. Archiv. Pharm. 1964, 297, 623.
(13) In unpublished work, treatment of 4-quinolone with p-tolyl
isocyanate under similar conditions gave 4-p-tolylaminoquinoline in
71% yield.
The structure of 6 was confirmed by X-ray crystal-
lography (Figure S3). Once again the NH group is
(14) (a) Katritzky, A. R.; Rachwal, S.; Offerman, R. J .; Najzarek,
Z.; Yagoub, A. K.; Zhang, Y. Chem. Ber. 1990, 123, 1545. (b) Katritzky,
A. R.; Stevens, C. V.; Zhang, G.-F.; J iang, J .; Kimpe, N. Heterocycles
1995, 40, 231.
(15) Saito, T.; Nakane, M.; Miyazaki, T.; Motoki, S. J . Chem. Soc.,
Perkin Trans. 1 1989, 2140.
(16) Molina, P.; Alcantara, J .; Lopez-Leonardo, C. Tetrahedron 1997,
53, 3281.

Reactions of Acylbenzotriazoles with Aryl Isocyanates
J . Org. Chem., Vol. 65, No. 23, 2000 8071
Sch em e 3
Sch em e 4
involved in an intramolecular hydrogen bond to the
adjacent carbonyl oxygen.
Sch em e 5
Ben z[b]-1,8-n a p h th yr id in e. Acetoacetylbenzotriazole
1d when heated with an excess of phenyl isocyanate gave
benz[b]-1,8-naphthyridine 7 in 83% yield (Scheme 3). The
mechanism of formation of benz[b]-1,8-naphthyridine 7
is more complex and appears to involve more steps than
the formation of quinolines 2 and 5. A plausible mech-
anism depicted in Scheme 3 involves the formation of
intermediate 8, which is then transformed into imine
species 9. The intermediate 9 reacts further with isocy-
anate to form the intermediate 10, which upon annula-
tion with formal loss of aniline (isolated from the reaction
mixture in the form of the N,N′-diphenylurea) followed
by further reaction with another molecule of isocyanate
affords benz[b]-1,8-naphthyridine 7.
mentation of the benzotriazole moiety10d,e and formation
of the pyridine ring within 12 and 14.
This method is advantageous in comparison with the
earlier reported synthesis of benz[b]-1,8-naphthyridines
from 2-chloroquinoline-3-aldehyde in 22-59% yields.17
This approach potentially provides access to a wider
range of substitution along with good yields and is an
advantageous alternative to previously reported conden-
sations of aryl isocyanates with anthranilic acid.1a
P h en a n th r id in e. 1-Benzoylbenzotriazole 1e readily
reacts with 2 equiv of p-methoxyphenyl isocyanate to
afford phenanthridine 12 in 82% yield (Scheme 4).1g,18a,b
Compound 14 was similarly obtained in 43% yield from
1-(2-thiophenoyl)benzotriazole derivative 1f. In contrast,
1-(2-furanoyl)benzotriazole afforded the corresponding
1-imidoylbenzotriazole derivative. The structure of 12
was established by X-ray analysis (Figure S4), while that
of 14 was assigned from spectroscopic data. Compound
12 crystallizes in the monoclinic space group P21/c, with
two independent molecules in the asymmetric unit, which
differ only in the conformations of the anisyl rings.
Since 1-acylbenzotriazoles 1e,f lack R-protons, the
formation of ketenes or their amino analogues is ex-
cluded. Thus, the formation of quinoline rings in 12 and
14 proceeds via a different mechanism. It most likely
involves formation of the corresponding imidoylbenzo-
triazole species 11 and 13 followed by a thermal frag-
In d olo[2,3-b]q u in olin e. When 1-cinnamoylbenzo-
triazole 1g was heated with 2 equiv of phenyl isocyanate,
indolo[2,3-b]quinoline 151g was isolated in 59% yield
(Scheme 5). The structure of 15 was established by X-ray
analysis (Figure S5). In this case, the NH hydrogen is
involved in an intramolecular hydrogen bond to the
quinoline nitrogen. This rearrangement most likely
proceeds via the initial formation of the corresponding
imidoyl benzotriazole derivative 16 followed by electro-
cyclic cyclization to yield 17. Finally, thermal decomposi-
tion of the benzotriazolyl moiety in 17 and cyclization of
the resulting radical 18 affords product 15. There are
mechanistic similarities between this reaction and some
of those earlier reported.1g However, in contrast to Wang’s
synthesis of indolo[2,3-b]quinoline, our approach is based
on a more readily accessible starting material and is also
two steps shorter.
(17) Meth-Cohn, O.; Tarnowski, B. Tetrahedron Lett. 1980, 21, 3721.
(18) (a) Saito, T.; Ohmori, H.; Ohkubo, T.; Motoki, S. J . Chem. Soc.,
Chem. Commun. 1993, 24, 1802. (b) Schmittel, M.; Steffen, J .-P.;
Engels, B.; Lennartz, C.; Hanrath, M. Angew. Chem., Int. Ed. Engl.
1998, 37, 2371.
In conclusion, we have demonstrated that five distinct
types of N-acylbenzotriazoles can react with isocyanates
to provide synthetic approaches to quinolines, pyrimi-

8072 J . Org. Chem., Vol. 65, No. 23, 2000
Katritzky et al.
Calcd for C10H11N3O: C, 63.48; H, 5.86; N, 22.21. Found: C,
63.26; H, 5.92; N, 22.33.
dino[5,4-c]quinolines, benz[b]-1,8-naphthyridine, phenan-
thridines, and indolo[2,3-b]quinolines, respectively.
2,4-Dia n ilin o-3-eth ylqu in olin e (2a ): 86% yellow hexago-
1
nal crystals; mp 171-172 °C; H NMR δ 1.21 (t, 3H, J ) 7.5
Exp er im en ta l Section
Hz), 2.72 (q, 2H, J ) 7.5 Hz), 5.60 (s, 1H, D2O exchangeable),
6.62 (s, 1H, D2O exchangeable), 6.62 (d, 2H, J ) 7.5 Hz), 6.82
(t, 1H, J ) 7.2 Hz), 7.05 (t, 1H, J ) 7.2 Hz), 7.13-7.20 (m,
3H), 7.38 (t, 2H, J ) 8.4 Hz), 7.51 (t, 1H, J ) 8.1 Hz), 7.67 (d,
1H, J ) 8.1 Hz), 7.84 (d, 1H, J ) 8.4 Hz), 7.85 (d, 2H, J ) 8.1
Hz); 13C NMR δ 13.0, 19.6, 115.1, 119.6, 119.7, 121.1, 122.0,
122.2, 123.0, 123.4, 127.4, 128.9, 129.0, 129.3, 140.6, 142.9,
146.0, 146.9, 152.8. Anal. Calcd for C23H21N3: C, 81.38; H, 6.24;
N, 12.38. Found: C, 81.19; H, 6.38; N, 12.40.
Gen er a l Meth od s. Melting points were determined on a
capillary melting point apparatus equipped with a digital
thermometer. NMR spectra were taken in CDCl3 with tetra-
methylsilane as the internal standard for 1H (300 MHz) or
solvent as the internal standard for 13C (75 MHz). THF was
distilled from sodium/benzophenone under nitrogen immedi-
ately prior to use. All reactions with air-sensitive compounds
were carried out under an argon atmosphere. Column chro-
matography was conducted with silica gel 230-400 mesh.
Gen er a l P r oced u r e for th e P r ep a r a tion of Com p ou n d s
1a -d ,f. To a solution of 0.1 mol of acyl chloride and 11.9 g of
benzotriazole in 300 mL of methylene chloride was added a
mixture of 11.0 g of triethylamine and 50 mL of methylene
chloride at 0-20 °C dropwise over 30 min. The mixture was
refluxed for 4 h, cooled to room temperature, and washed with
100 mL of water, 50 mL of saturated NH4Cl, 50 mL of 10%
NaHCO3, and 100 mL of water. The organic layer was dried
over anhydrous MgSO4, and the filtrate was diluted with
hexane (about 60 mL) and was kept at 0 °C overnight. The
desired product was isolated as colorless crystals. The analyti-
cally pure acyl-1-benzotriazoles were obtained by re-crystal-
lization from 2-propanol.
6-Meth yl-N2,N4-bis(4-m eth yp h en yl)-3-(1,3,3-tr im eth yl-
bu tyl)qu in olin e-2,4-d ia m in e (2b): 83%, glassy solid; 1H
NMR δ 0.84 (s, 9H), 1.34 (d, 3H, J ) 7.3 Hz), 1.60 (dd, 1H, J
) 5.7, 13.2 Hz), 1.85 (dd, 1H, J ) 5.7, 13.2 Hz), 2.27 (s, 3H),
2.36 (br s, 6H), 3.74 (br s, 1H), 5.48 (br s, 1H), 6.59 (d, 2H, J
) 8.2 Hz), 6.62 (br s, 1H), 6.99 (d, 2H, J ) 8.2 Hz), 7.18 (d,
2H, J ) 8.2 Hz), 7.34 (d, 1H, J ) 8.1 Hz), 7.47 (br s, 1H), 7.71
(d, 2H, J ) 8.2 Hz), 7.75 (br s, 1H); 13C NMR δ 20.5, 20.8,
21.6, 27.2, 29.5, 31.9, 50.4, 115.4, 119.5, 122.1, 126.1, 126.9,
128.8, 129.3, 129.8, 130.8, 131.3, 132.5, 138.2, 141.7, 144.1,
145.2, 150.0, 152.8. Anal. Calcd for C31H37N3: N, 9.30; Found:
N, 9.22
2,4-Di(4-m eth ylp h en yla m in o)-3-eth yl-6-m eth ylqu in o-
lin e (2c): 76% yellow needles; mp 165-166 °C; 1H NMR δ
1.19 (t, 3H, J ) 7.8 Hz), 2.26 (s, 3H), 2.34 (s, 3H), 2.36 (s, 3H),
2.72 (q, 2H, J ) 7.5 Hz), 5.56 (br s, 1H), 6.58 (d, 2H, J ) 8.1
Hz), 6.98 (d, 2H, J ) 8.1 Hz), 7.16 (d, 2H, J ) 8.1 Hz), 7.25 (s,
1H), 7.33 (dd, 1H, J ) 1.7, 7.6 Hz), 7.45 (br s, 1H), 7.70 (t, 3H,
J ) 8.4 Hz); 13C NMR δ 13.2, 19.9, 20.7, 21.0, 21.8, 115.5,
120.0, 120.8, 122.1, 122.4, 127.4, 129.3, 129.6, 130.0, 131.1,
131.8, 132.7, 138.5, 143.1, 143.9, 145.5, 152.8; HRMS calcd
for C26H28N3 382.2283, found 382.2244.
Compounds 1e,g were prepared according to published
procedures.19a,b,20
Gen er a l P r oced u r e for th e P r ep a r a tion of Com p ou n d s
2a ,b, 5a ,b, 6, 7, 12, 14, a n d 15. The mixture of 3 mmol of
1-acyl-benzotriazole and 5-10 mmol of aryl isocyanate was
heated at 210 °C for 24 h (unless mentioned otherwise) in a
50 mL sealed tube and then cooled to room temperature. The
reaction mixture was subjected to column chromatography
with hexane/ethyl acetate (6/1∼10/1) to give the corresponding
product. Analytically pure product was obtained as yellow
crystals by re-crystallization from methylene chloride-ethanol
mixture.
Bu tyr yl-1-ben zotr ia zole (1a ): 92% white needles; mp 62-
63 °C; 1H NMR δ 1.08 (t, 3H, J ) 7.5 Hz), 1.82-1.90 (m, 2H),
3.40 (t, 2H, J ) 7.2 Hz), 7.60 (t, 1H, J ) 7.2 Hz), 7.75 (t, 1H,
J ) 7.2 Hz), 8.18 (d, 1H, J ) 8.4 Hz), 8.20 (d, 1H, J ) 8.4 Hz);
13C NMR δ 13.3, 17.0, 36.6, 113.7, 119.7, 126.0, 130.3, 145.3,
172.0. Anal. Calcd for C10H11N3O: C, 63.48; H, 5.86; N, 22.21.
Found: C, 63.78; H, 6.07; N, 22.42.
5-An ilin o-1,3-d ip h en ylp yr im id o[5,4-c]q u in olin e-2,4-
(1H,3H)-d ion e (5a ): 66% yellow needles; mp 272-273 °C; 1H
NMR δ 6.92-6.98 (m, 1H), 7.14 (d, 2H, J ) 7.8 Hz), 7.21 (t,
1H, J ) 7.2 Hz), 7.30-7.58 (m, 15H), 11.92 (br s, 1H); 13C NMR
δ 94.1, 115.9, 122.7, 123.5, 125.8, 126.6, 128.2, 128.6, 128.8,
129.1, 129.2, 129.3, 129.4, 132.3, 134.7, 136.5, 141.4, 149.9,
150.4, 150.6, 155.2, 165.3. Anal. Calcd for C29H20N4O2: N,
12.27. Found: N, 11.93.
3-(4-Meth ylp h en yl)-9-m eth yl-1-(4-m eth ylp h en yl)-5-(4-
tolu id in o)[5,4-c]qu in olin e-2,4(1H,3H)-d ion e (5b): 68% yel-
1
low prisms; mp 229-230 °C; H NMR δ 1.98 (s, 3H), 2.33 (s,
3H), 2.42 (s, 3H), 2.44 (s, 3H), 6.54-6.55 (br, 1H), 7.14 (d, 2H,
J ) 8.4 Hz), 7.22-7.27 (m, 6H), 7.33 (t, 3H, J ) 8.1 Hz), 7.58
1-(1H-1,2,3-Ben zotr iazol-1-yl)-1,3-bu tan edion e (1d): 91%
white prisms; mp 69-70 °C (lit.21 mp 69 °C), as 2:1 mixture of
(d, 1H, J ) 8.1 Hz), 7.80 (d, 2H, J ) 8.1 Hz), 11.11 (s, 1H); 13
C
1
tautomers; H NMR (C6D6) δ 1.53 (d, 1.8H, J ) 4.1 Hz), 1.67
NMR δ 20.9, 21.2, 21.3, 21.4, 97.7, 112.6, 120.6, 125.7, 127.7,
127.9, 128.6, 129.2, 130.1, 130.3, 130.9, 131.9, 132.0, 134.1,
137.5, 137.7, 139.2, 148.6, 150.0, 151.1, 151.6, 163.9. Anal.
Calcd for C33H28N4O2: C, 77.32; H, 5.51; N, 10.93. Found: C,
77.46; H, 5.86; N, 10.91.
(d, 1.2 H, J ) 7.3 Hz), 3.81 (d, 0.6H, J ) 9.2 Hz), 6.44 (s, 0.6H),
6.87-7.11 (m, 1.2H), 7.72 (dd, 0.4H, J ) 7.6, 0.6 Hz), 7.80 (d,
0.6H, J ) 8.2 Hz), 8.11-8.12 (m, 1H), 13.29 (br s, 0.6H); 13C
NMR (C6D6) δ 21.6, 29.7, 50.6, 90.6, 114.4, 114.8, 120.3, 125.8,
126.2, 127.7, 128.0, 128.3, 129.9, 130.3, 131.1, 131.4, 146.7,
146.9, 166.1, 169.6, 182.0, 182.1, 199.0.
5-An ilin o-1,3-d ip h en ylp yr im id o[4,5-b ]q u in olin e-2,6-
(1H,3H)-d ion e (6): 86% yellow cubic crystals; mp 272-273
1-(2-Th iop h en oyl)b en zot r ia zole (1f): 89% colorless
1
°C; H NMR δ 6.75 (t, 1H, J ) 7.8 Hz), 6.86 (d, 1H, J ) 8.1
1
needles; mp 175-176 °C; H NMR δ 7.27 (t, 1H, J ) 3.9 Hz),
Hz), 7.06-7.12 (m, 1H), 7.30-7.61 (m, 13 H), 7.73 (d, 1H, J )
8.4 Hz), 7.96 (d, 2H, J ) 7.8 Hz), 11.24 (br s, 1H); 13C NMR δ
98.2, 113.1, 120.8, 120.9, 122.1, 123.1, 126.4, 128.3, 128.4,
128.9, 129.0, 129.2, 129.4, 129.5, 129.9, 132.5, 134.7, 140.1,
140.4, 149.3, 151.8, 152.1, 163.9. Anal. Calcd for C29H20N4O2:
C, 76.30; H, 4.42; N, 12.27. Found: C, 74.67; H, 4.31; N, 11.94.
1,3,6-Tr iph en yl-2-(ph en ylim in o)-2,3-dih ydr o-1H-ben zo-
[b]pyr im ido[4,5,6-de][1,8] n aph th yr idin -5(6H)-on e (7): 78%
yellow block crystals; mp 290-291 °C; 1H NMR δ 5.29 (s, 1H),
7.03-7.67 (m, 21H), 7.79 (ss, 1H, J ) 8.7, 0.9 Hz), 7.90 (dd,
1H, J ) 8.9 Hz, J ) 1.2 Hz), 12.67 (s, 1H); 13C NMR δ 100.5,
117.7, 121.8, 122.5, 123.3, 123.7, 125.4, 126.8, 127.2, 128.2,
128.3, 129.1, 129.5, 129.6, 130.8, 132.2, 138.5, 142.5, 144.0,
7.53 (t, 1H, J ) 8.4 Hz), 7.68 (t, 1H, J ) 6.9 Hz), 7.88 (dd, 1H,
J ) 4.8, 1.2 Hz), 8.15 (d, 1H, J ) 8.4 Hz), 8.39 (d, 1H, J ) 8.4
Hz), 8.57 (dd, 1H, J ) 3.9, 1.2 Hz); 13C NMR δ 114.8, 120.2,
126.3, 128.1, 130.5, 132.1, 133.4, 137.3, 138.5, 145.8, 159.2.
Anal. Calcd for C11H7N3OS: C, 57.63; H, 3.08; N, 18.33.
Found: C, 57.78; H, 3.13; N, 18.39.
1-Acetyl-5,6-d im eth ylben zotr ia zole (1h ): 61% white
prisms; mp 97-98 °C; 1H NMR δ 2.41 (s, 3H), 2.43 (s, 3H),
2.97 (s, 3H), 7.80 (s, 1H), 8.00 (s, 1H); 13C NMR δ 20.4, 20.9,
23.2, 113.9, 119.2, 129.8, 135.8, 140.9, 145.29, 169.6. Anal.
(19) (a) Kreutzberger, A.; Dietz, E.; Tetrahedron Lett. 1970, 1457.
(b) Katritzky, A. R.; Pastor, A.; Voronkov, M. J . Heterocycl. Chem. 1999,
36, 777.
(20) Katritzky, A. R.; Shobana, N.; Pernak, J .; Afridi, A. S.; Fan,
W.-Q. Tetrahedron 1992, 48, 7817.
(21) Katritzky, A. R.; Rachwal, S.; Rachwal, B. J . Chem. Soc., Perkin
Trans. 1 1990, 1717.
148.1, 148.5,152.5, 153.0,154.6, 166.3; HRMS calcd for C37H25
-
N5O2 556.2153, found 556.2137. Anal. Calcd for C37H25N5O2:
N, 12.60. Found: N, 12.36.
N-(4-Meth oxyph en yl)-6-ph en a n th r idin a m in e (12): 82%
1
yellow needles; mp 165-166 °C; H NMR δ 3.81 (s, 3H), 6.93

Reactions of Acylbenzotriazoles with Aryl Isocyanates
J . Org. Chem., Vol. 65, No. 23, 2000 8073
(t, 2H, J ) 8.4 Hz), 7.14 (s, 1H), 7.36 (t, 1H, J ) 7.2 Hz), 7.53-
7.52 (m, 2H), 7.73-7.83 (m, 4H), 7.94 (d, 1H, J ) 7.8 Hz), 8.34
(d, 1H, J ) 8.1 Hz), 8.53 (d, 1H, J ) 8.1 Hz); 13C NMR δ 55.5,
114.1, 119.5, 121.7, 122.2, 122.9, 123.3, 127.1, 127.6, 128.8,
130.2, 133.4, 134.2, 151.3, 155.4. Anal. Calcd for C20H16N2O:
C, 79.98; H, 5.37; N, 9.33. Found: C, 79.74; H, 5.58; N, 9.36.
N,N′-Bis(4-m et h ylp h en yl)-N-t h ien o[2,3-c]q u in olin -4-
ylu r ea (14): 43% yellow needles; mp 172-173 °C; 1H NMR δ
2.61 (s, 3H), 2.68 (s, 3H), 7.31 (dd, 1H, J ) 3.6, 4.8 Hz), 7.46
(d, 2H, J ) 8.1 Hz), 7.54 (d, 2H, J ) 7.8 Hz), 7.61 (dd, 2H, J
) 5.1, 1.6 Hz), 7.71 (t, 1H, J ) 8.4 Hz), 7.96-8.04 (m, 5H),
8.14 (dd, 1H, J ) 1.2, 2.4 Hz); 13C NMR δ 20.9, 21.3, 113.9,
119.1, 121.0, 125.2, 127.8, 128.4, 129.4, 130.9, 133.2, 133.5,
133.7, 135.4, 136.1, 137.1, 139.8, 148.3, 157.3. Anal. Calcd for
and refinement parameters for the six structures are listed in
Table S1. Data were collected with a Siemens SMART CCD
area detector, using graphite-monochromatized Mo KR radia-
tion (λ ) 0.710 73 Å). The structures were solved by direct
methods using SHELXS22 and refined on F2, using all data,
by full-matrix least-squares procedures with SHELXTL.23 CH
hydrogen atoms were included in calculated positions with
isotropic displacement parameters 1.2 times the isotropic
equivalent of their carrier atoms, while the NH hydrogens
were located from difference Fourier syntheses and their
2
positions refined. The functions minimized were ∑w(Fo
-
Fc2)2, with w ) [σ2(Fo2) + (aP)2 + bP]-1, where P ) [max(Fo)2
+ 2Fc2]/3.
Su p p or tin g In for m a tion Ava ila ble: Perspective views
(Figures S1-S5), crystal data, data collection and refinement
parameters, full tables of atom coordinates, bond lengths and
angles, and thermal displacement parameters (Tables S1-S25)
for X-ray crystal structures of 2a , 5a ,b, 6, 12, and 15. This
material is available free of charge via the Internet at
http://pubs.acs.org.
C
26H21N3OS: N, 9.92. Found: N, 10.22.
N-1,1-Dip h en yl-6H -in d olo[2,3-b]q u in olin e-6-ca r b oxa -
1
m id e (15): 59% yellow needles; mp 189-190 °C; H NMR δ
6.87 (d, 1H, J ) 7.2 Hz), 7.05 (t, 1H, J ) 7.8 Hz), 7.16 (t, 1H,
J ) 7.2 Hz), 7.40-7.47 (m, 6H), 7.60-7.63 (m, 3H), 7.66-7.75
(m, 2H), 7.82 (d, 2H, J ) 7.82 Hz), 8.12 (d, 1H, J ) 8.1 Hz),
8.79 (d, 1H, J ) 8.1 Hz), 13.1 (br s, 1H); 13C NMR δ 116.9,
117.6, 120.2, 121.7, 122.3, 123.0, 123.8, 125.0, 125.1, 126.3,
127.5, 128.9, 129.0, 129.1, 129.2, 129.6, 135.3, 138.4, 140.5,
143.3, 144.0, 150.5, 150.8. Anal. Calcd for C28H19N3O: N, 10.16.
Found: N, 10.10.
J O0009604
(22) Sheldrick, G. M. Acta Crystallogr., Sect. A 1990, 46, 467.
(23) Sheldrick, G. M. SHELXTL, Bruker Analytical X-ray Systems,
1997.
X-r a y Cr ysta llogr a p h y. The crystal data, data collection,