Facile and one-pot synthesis of 1,2-dihydroquinazolin-4(3H)-ones via tandem intramolecular pinner/dimroth rearrangement

Article abstract of DOI:10.1080/00397910902908822

An efficient synthetic method for the preparation of quinazolin-4-one derivatives was designed. The facile condensation of aromatic o-aminonitriles with aromatic aldehydes catalyzed by Lewis acid give 1,2-dihydroquinazolin-4(3H) -ones in moderate to good

Full text of DOI:10.1080/00397910902908822

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Facile and One-Pot Synthesis of 1,2-
Dihydroquinazolin-4(3H)-ones via
Tandem Intramolecular Pinner/Dimroth
Rearrangement
Jian-Hong Tang a , Da-Xin Shi a , Li-Jun Zhang b , Qi Zhang a & Jia-
Rong Li a
a School of Chemical Engineering and Environment , Beijing Institute
of Technology , Beijing, China
b School of Chemistry and Chemical Engineering , Tianjin University
of Technology , Tianjin, China
Published online: 04 Feb 2010.
To cite this article: Jian-Hong Tang , Da-Xin Shi , Li-Jun Zhang , Qi Zhang & Jia-Rong Li (2010) Facile
and One-Pot Synthesis of 1,2-Dihydroquinazolin-4(3H)-ones via Tandem Intramolecular Pinner/Dimroth
Rearrangement, Synthetic Communications: An International Journal for Rapid Communication of
Synthetic Organic Chemistry, 40:5, 632-641, DOI: 10.1080/00397910902908822
To link to this article: http://dx.doi.org/10.1080/00397910902908822
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Synthetic Communications1, 40: 632–641, 2010
Copyright # Taylor & Francis Group, LLC
ISSN: 0039-7911 print=1532-2432 online
DOI: 10.1080/00397910902908822
FACILE AND ONE-POT SYNTHESIS OF
1,2-DIHYDROQUINAZOLIN-4(3H)-ONES
VIA TANDEM INTRAMOLECULAR
PINNER/DIMROTH REARRANGEMENT
Jian-Hong Tang,1 Da-Xin Shi,1 Li-Jun Zhang,2 Qi Zhang,1
and Jia-Rong Li1
1School of Chemical Engineering and Environment, Beijing Institute of
Technology, Beijing, China
2School of Chemistry and Chemical Engineering, Tianjin University of
Technology, Tianjin, China
An efficient synthetic method for the preparation of quinazolin-4-one derivatives was
designed. The facile condensation of aromatic o-aminonitriles with aromatic aldehydes
catalyzed by Lewis acid give 1,2-dihydroquinazolin-4(3H)-ones in moderate to good yields
under refluxing dimethylformamide.
Keywords: Aromatic aldehyde; aromatic o-aminonitrile; catalyst; cyclocondensation; one-pot synthesis
INTRODUCTION
1,2-Dihydroquinazolin-4(3H)-ones are important and useful nitrogen-containing
heterocycles because of their diverse biological activities. They have been widely used as
antitumoragents, a1-adrenoceptorsantagonists, plant growth regulators, diuretics, and
herbicides.[1] Some dihydroquinazolinones also show potential applications in
flat-panel display as electro-luminescence material sandwiched in organic light-emitting
devices.[2] The main synthetic approaches to 1,2-dihydroquinazolin-4(3H)-ones
consist of preliminary amidation of 2-amino-benzonitrile, 2-amino-benzoic acid, or
its derivatives followed by oxidative ring closure under basic conditions.[3] Other meth-
ods involve cycloaddition of anthranilic acid derivatives with a diverse range of
substrates including imidates and iminohalides and the aza–Witting reactions of
a-azido-substituted aromatic amides.[4,5] However, some of these methods are associa-
ted with drawbacks such as multistep procedures, costly reagents, harsh reaction con-
ditions, and poor yields. Thus, there is still a need to develop efficient methods for the
synthesis of dihydroquinazolinones.
Received January 11, 2009.
Address correspondence to Jia-Rong Li, School of Chemical Engineering and Environment,
Beijing Institute of Technology, Beijing 100081, China. E-mail: jrli@bit.edu.cn
632

SYNTHESIS OF 1,2-DIHYDROQUINAZOLIN-4(3H)-ONES
633
Aromatic o-aminonitrile is
a versatile synthon for the synthesis of
nitrogen-containing fused heterocycles 5,[6] such as pyrimidine,[7] quinazoline,[8,9]
quinazolinone,[10,11] and quin[3,4-a]carbazole.[12] In continuation of our previous
work on the synthesis of a variety of nitrogen-containing heterocycles from
2-aminobenzonitriles,[13] we report herein a convenient and one-pot synthesis of
1,2-dihydroquinazolin-4(3H)-ones from the cyclocondensation of aromatic
o-aminonitriles with aromatic aldehydes using anhydrous ZnCl2 as the catalyst.
The reaction of 2-amino-5-nitrobenzonitrile 1a with 3-nitrobenzoaldehyde 2b
was chosen as a model (Scheme 1). After different conditions were screened, we were
delighted to find that the 1,2-dihydroquinazolin-4(3H)-one derivative 3b was
obtained from this reaction with ZnCl2 as catalyst in a suitable boiling solvent. After
screening solutions, we found dimethylformamide (DMF) was the best solvent and
dimethylsulfoxide (DMSO) was also suitable for this annulation, but no product was
afforded in nonpolar solvents such as toluene and xylene.
With the optimized reaction conditions in hand, various aldehydes 2, including
aromatic or heteroaromatic aldehydes with either electron-donating or electron-
withdrawing substitutents, were subjected to react with 1 to investigate the reaction
scope, and the representative results are summarized in Table 1.
1,2-Dihydroquinazolin-4(3H)-one derivatives 3a–n (Table 1) were formed by
the reactions of aromatic o-aminonitriles with aldehydes in refluxed DMF in good
yields. The position and electronic nature of the substituent on the phenyl ring of
arylaldehydes had no relevance to quinazolinone yield. Although nitro- and meth-
oxy- substitutents have different electron effects on benzaldehydes, similar reaction
rate and yield were observed. Heteroaromatic aldehydes were also readily cyclized
with 1 to afford quinazolinones 3m–n in 72–77% yield. The new conversion pro-
ceeded better when o-aminonitriles 1 had electron-withdrawing substituents. The
structures of 3 were verified by instrument analysis, and 3l was also further eluci-
dated by x-ray crystallographic analysis (Fig. 1). Crystal data for 3l: chemical for-
mula, C14H11N3O3; formula weight, 269.26; temperature (K), 113(2); crystal
system, monoclinic; space group, Pnma; and unit cell dimension, a ¼ 1.09766(13)
nm, b ¼ 0.98626(9) nm, c ¼ 1.17636(14) nm, a ¼ 90.00, b ¼ 109.697(7)ꢀ, c ¼ 90ꢀ;
V ¼ 1.1990(2) nm3, Z ¼ 4, and DC ¼ 1.492 g cmꢁ3
.
On the basis of these observations, a possible mechanism was proposed
(Scheme 2). Addition of the amino group of the o-aminonitrile onto the carbonyl
of the aldehyde gave the key intermediate I. The hydroxyl group of intermediate I
then attacked the nitrile group (i.e., Pinner reaction[14]) to afford a benzoxazine II,
which subsequently rearranged (Dimroth rearrangement[15]) to give the product 3.
Scheme 1. Condensation of 2-amino-5-nitrobenzonitrile with 3-nitrobenzoaldehyde.

634
J.-H. TANG ET AL.
Table 1. Results of the reaction of o-aminonitriles with various aldehydes in DMFa
Entry
Product
R1
R2
R3
Time (h)
Yieldb (%)
1
2
3a
3b
3c
3d
3e
3f
H
H
H
H
H
Cl
Cl
H
H
H
H
H
H
H
NO2
NO2
NO2
NO2
NO2
H
C6H5
1.5
1
72
80
82
80
77
72
74
67
72
73
70
73
72
77
m-O2NC6H4
p-CH3OC6H4
p-ClC6H4
3
1
4
1
5
p- O2NC6H4
p- O2NC6H4
p-CH3OC6H4
p- O2NC6H4
o-HOC6H4
p-CH3OC6H4
p-Cl C6H4
1
6
2
7
3g
3h
3i
H
2
8
H
2.5
2.5
2.5
2.5
2.5
2.5
1
9
H
10
11
12
13
14
3j
H
3k
3l
H
H
m-O2NC6H4
furan-2-yl
pyridin-4-yl
3m
3n
NO2
NO2
aAll reactions were carried out using 1 (2.5 mmol), 2 (3.0 mmol), ZnCl2(3.0 mmol), and DMF (3 mL).
bIsolated yield.
Figure 1. Molecular structure of compound 3l. Crystal structure: Selected bond length (Aꢀ) and bond angles
(3l): O(1)–C(1) 1.2500(19), O(2)–N(3) 1.237(3), O(3)–N(3) 1.2247(19), N(1)–C(1) 1.346(2), N(1)–C(8)
1.465(2), N(2)–C(3) 1.374(2), N(2)–C(8) 1.456(2), C(1)–C(2) 1.479(2), C(2)–C(3) 1.410(2), C(1)–N(1)–C(8)
123.91(14), C(3)–N(2)–C(8) 119.55(13), O(3)–N(3)–O(2) 123.4(2), N(1)–C(1)–C(2) 116.11(14), C(3)–C(2)–
C(1) 119.07(14), N(2)–C(3)–C(2) 119.70(15), N(2)–C(8)–N(1) 108.72(13), N(2)–C(8)–C(9) 112.72(13), N(1)–
C(8)–C(9) 112.16(13).

SYNTHESIS OF 1,2-DIHYDROQUINAZOLIN-4(3H)-ONES
635
Scheme 2. Reaction of aromatic o-aminonitrile with aromatic aldehyde.
As an extension of the research, the reaction of 2-amino-benzonitrile 1a with
terephthalaldehyde 4 in the sealed reactor under the catalyst of ZnCl2 (0.1 mol) at
200ꢀC afforded the expected symmetrical bisquinazolinone derivatives 5 (Scheme 3).
CONCLUSION
Quinazolin-4(3H)-one derivatives were conveniently obtained by the cycliza-
tion of o-aminonitriles with carbonyl compounds using zinc chloride as the catalyst
of in DMF. The reaction scope is substantial, and a number of aryl aldehydes could
be successfully applied to react with o-aminonitriles to give quinazolinone com-
pounds with good yields. Currently work is actively under way to expand this syn-
thetic methodology to other valuable o-aminonitrile systems.
Scheme 3. Reaction of 2-amino-5-nitrobenzonitrile with terephthalaldehyde.

636
J.-H. TANG ET AL.
EXPERIMENTAL
General Procedure
o-Aminobenzonitrile 1 (2.5 mmol) and aldehydes (2.5 mmol) were added to a
solution of DMF (10 mL) and ZnCl2 (3.0 mmol). The mixture was heated at reflux
for the specified time (see Table 1). After completion of the reaction as indicated
by thin-layer chromatography (TLC; eluent: ethyl acetate), the cooled reaction mix-
ture was quenched with water (10 mL), and the precipitate was separated by fil-
tration. Then the residue was dispersed into water and titrated to pH 12–13 by
20% sodium hydroxide. After filtration, the products 3a–n were isolated by column
chromatography (200- to 300-mesh silica gel, ethyl acetate–petroleum 1:2).
6-Nitro-2-phenyl-1,2-dihydroquinazolin-4(3H)-one (3a)
1
Mp 264–265ꢀC; H NMR (400 MHz, DMSO-d6) dH: 6.02 (1H, t, J ¼ 1.7 Hz,
CH), 6.83 (1H, d, J ¼ 8.8 Hz, ArH), 7.39 (1H, t, J ¼ 7.2 Hz, ArH), 7.42 (2H, t,
J ¼ 7.2, 8.0 Hz, ArH), 7.49 (2H, d, J ¼ 8.0 Hz, ArH), 8.11 (1H, dd, J ¼ 2.8, 8.8 Hz,
ArH), 8.44 (1H, d, J ¼ 2.8 Hz, ArH), 8.57 (1H, s, NH), 8.75 (1H, s, NH). 13C
NMR (100 MHz, DMSO-d6) dC: 66.30, 112.64, 114.24, 124.18, 126.54 (2C), 128.65
(2C), 128.88, 128.97, 137.12, 141.09, 152.13, 161.28; MS (ESI): m=z (%) ¼ 270.1
(100) [M þ H]þ. IR (KBr): vmax 3385, 3166, 1690, 1618, 1530, 1329, 1140 cmꢁ1. Anal.
calcd. for C14H11N3O3: C, 62.45; H, 4.12; N, 15.61. Found: C, 62.28; H, 3.80;
N, 15.25.
6-Nitro-(3-nitrophenyl)-1,2-dihydroquinazolin-4(3H)-one (3b)
1
Mp 294–296ꢀC; H NMR (400 MHz, DMSO-d6) dH: 6.25 (1H, s, CH), 6.89
(1H, d, J ¼ 8.8 Hz, ArH), 7.75 (1H, t, J ¼ 8.0 Hz, ArH), 7.94 (1H, d, J ¼ 8.0 Hz,
ArH), 8.14 (1H, dd, J ¼ 2.8, 8.8 Hz, ArH), 8.26–8.27 (1H, m, J ¼ 1.6 Hz, ArH),
8.35 (1H, t, J ¼ 1.6 Hz, ArH), 8.44 (1H, d, J ¼ 2.8 Hz, ArH), 8.73 (1H, s, NH),
8.96 (1H, s, NH). 13C NMR (100 MHz, DMSO-d6) dC: 65.03, 112.69, 114.55,
121.38, 123.69, 124.16, 129.11, 130.45, 133.02, 137.50, 143.45, 147.80, 151.78,
161.19; MS (ESI): m=z (%) ¼ 315.4 (100) [M þ H]þ. IR (KBr): vmax 3321, 3191,
1685, 1618, 1532, 1324 cmꢁ1. Anal. calcd. for C14H10N4O5: C, 53.51; H, 3.21;
N, 17.82. Found: C, 53.22; H, 3.27; N, 17.72.
6-Nitro-2-(4-methoxyphenyl)-1,2-dihydroquinazolin-4(3H)-one (3c)
1
Mp 242–243ꢀC; H NMR (400 MHz, DMSO-d6) dH: 3.75 (3H, s, CH3), 5.97
(1H, s, CH), 6.82 (1H, d, J ¼ 8.8 Hz, ArH), 6.98 (2H, d, J ¼ 8.4 Hz, ArH), 7.39
(2H, d, J ¼ 8.4 Hz, ArH), 8.11 (1H, dd, J ¼ 2.8, 8.8 Hz, ArH), 8.43 (1H, d, J ¼ 2.8 Hz,
Hz, ArH), 8.50 (1H, s, NH), 8.68 (1H, s, NH). 13C NMR (100 MHz, DMSO-d6) dC:
55.19, 65.91, 112.62, 113.90 (2C), 114.20, 124.16, 127.94 (2C), 128.93, 132.94, 136.99,
152.19, 159.67, 161.36; MS (ESI): m=z (%) ¼ 300.1 (100) [M þ H]þ. IR (KBr): vmax
3385, 3162, 1660, 1620, 1512, 1309 cmꢁ1. Anal. calcd. for C15H13N3O4: C, 60.19;
H, 4.38; N, 14.04. Found: C, 60.05; H, 4.40; N, 14.11.

SYNTHESIS OF 1,2-DIHYDROQUINAZOLIN-4(3H)-ONES
637
2-(4-Chlorophenyl)-6-nitro-1,2-dihydroquinazolin-4(3H)-one (3d)
1
Mp 263–265ꢀC; H NMR (400 MHz, DMSO-d6) dH: 6.06 (1H, s, CH), 6.84
(1H, d, J ¼ 8.8 Hz, ArH), 7.50 (4H, s, ArH), 8.13 (1H, dd, J ¼ 2.8, 8.8 Hz, ArH),
8.43 (1H, d, J ¼ 2.8 Hz, ArH), 8.59 (1H, s, NH), 8.80 (1H, s, NH). 13C NMR
(100 MHz, DMSO-d6) dC: 65.49, 112.62, 114.32, 124.13, 128.45 (2C), 128.62 (2C),
128.99, 133.40, 137.23, 140.05, 151.96, 161.20; MS (ESI): m=z (%) ¼ 304.4 (100)
[M þ H]þ. IR (KBr): vmax 3366, 3180, 1692, 1615, 1492, 1328 cmꢁ1. Anal. calcd.
for C14H10N3O3Cl: C, 55.37; H, 3.32; N, 13.83. Found: C, 55.59; H, 3.62; N, 13.44.
6-Nitro-2-(4-nitrophenyl)-1,2-dihydroquinazolin-4(3H)-one (3e)
1
Mp 263–265ꢀC; H NMR (400 MHz, DMSO-d6) dH: 6.21 (1H, s, CH), 6.87
(1H, d, J ¼ 8.8 Hz, ArH), 7.73 (2H, d, J ¼ 8.4 Hz, ArH), 8.13 (1H, dd, J ¼ 2.8,
8.8 Hz, ArH), 8.29 (2H, d, J ¼ 8.4 Hz, ArH), 8.43 (1H, d, J ¼ 2.8 Hz, ArH), 8.72
(1H, s, NH), 8.96 (1H, s, NH). 13C NMR (100 MHz, DMSO-d6) dC: 65.14, 112.63,
114.49, 123.92 (2C), 124.16, 127.80 (2C), 129.11, 137.44, 147.66, 148.29, 151.73,
161.09; MS (ESI): m=z (%) ¼ 315.4 (100) [M þ H]þ. IR (KBr): vmax 3350, 3084,
1690, 1621, 1522, 1330 cmꢁ1. Anal. calcd. for C14H10N4O5: C, 53.51; H, 3.21; N,
17.82. Found: C, 53.33; H, 3.31; N, 17.46.
7-Chloro-2-(4-nitrophenyl)-1,2-dihydroquinazolin-4(3H)-one (3f)
1
Mp 243–244ꢀC; H NMR (400 MHz, DMSO-d6) dH: 5.99 (1H, s, CH), 6.70
(1H, dd, J ¼ 2.0, 8.4 Hz, ArH), 6.82 (1H, d, J ¼ 2.0 Hz, ArH), 7.60 (2H, d, J ¼ 8.4 Hz,
Hz, ArH), 7.73 (2H, d, J ¼ 8.4 Hz, ArH), 8.26 (1H, s, NH), 8.27 (1H, d, J ¼ 8.4 Hz,
ArH), 8.66 (1H, s, NH). 13C NMR (100 MHz, DMSO-d6) dC: 65.22, 113.59, 113.63,
117.43, 123.72 (2C), 127.95 (2C), 129.43, 138.09, 147.52, 148.20, 148.97, 162.42; MS
(ESI): m=z (%) ¼ 304.0 (100) [M þ H]þ. IR (KBr): vmax 3355, 3282, 1660, 1609, 1521,
1351 cmꢁ1. Anal. calcd. for C14H10N3O3Cl: C, 55.37; H, 3.32; N, 13.84. Found:
C, 55.72; H, 3.39; N, 13.86.
7-Chloro-2-(4-methoxyphenyl)-1,2-dihydroquinazolin-4(3H)-one (3g)
1
Mp 221–223ꢀC; H NMR (400 MHz, DMSO-d6) dH: 3.75 (3H, s, CH3), 5.76
(1H, s, CH), 6.69 (1H, dd, J ¼ 2.0, 8.4 Hz, ArH), 6.78 (1H, d, J ¼ 2.0 Hz, ArH),
6.96 (2H, dd, J ¼ 1.6, 6.8 Hz, ArH), 7.29 (1H, s, NH), 7.41 (2H,dd, J ¼ 1.6, 6.8 Hz,
ArH), 7.60 (1H, d, J ¼ 8.4 Hz, ArH), 8.32 (1H, s, NH). 13C NMR (100 MHz,
DMSO-d6) dC: 55.21, 66.23, 113.45, 113.71, 113.76 (2C), 117.01, 128.17 (2C),
129.36, 133.17, 137.79, 148.94, 159.56, 162.84; MS (ESI): m=z (%) ¼ 289.0 (100)
[M þ H]þ. IR (KBr): vmax 3299, 3181, 1653, 1609, 1512 cmꢁ1. Anal. calcd. for
C15H13N2O2Cl: C, 62.40; H, 4.54; N, 9.70. Found: C, 62.00; H, 4.55; N, 9.94.
2-(4-Nitrophenyl)-1,2-dihydroquinazolin-4(3H)-one (3h)
1
Mp 198–200ꢀC; H NMR (400 MHz, DMSO-d6) dH: 5.91 (1H, s, CH), 6.68
(1H, t, J ¼ 7.6 Hz, ArH), 6.76 (1H, d, J ¼ 8.0 Hz, ArH), 7.26 (1H, t, J ¼ 7.6 Hz,

638
J.-H. TANG ET AL.
ArH), 7.33 (1H, s, NH), 7.60 (1H, d, J ¼ 8.0 Hz, ArH), 7.73 (2H, d, J ¼ 8.4 Hz, ArH),
8.25 (2H, d, J ¼ 8.4 Hz, ArH), 8.51 (1H, s, NH). 13C NMR (100 MHz, DMSO-d6) dC:
65.76, 115.02, 115.38, 117.92, 124.02 (2C), 127.86, 128.48 (2C), 134.00, 147.68,
147.91, 149.81, 163.71; MS (ESI): m=z (%) ¼ 270.1 (100) [M þ H]þ. IR (KBr): vmax
3389, 3282, 1647, 1615, 1520, 1349 cmꢁ1. Anal. calcd. for C14H11N3O3: C, 62.45;
H, 4.12; N, 15.61. Found: C, 62.21; H, 4.51; N, 15.36.
2-(2-Hydroxyphenyl)-1,2-dihydroquinazolin-4(3H)-one (3i)
1
Mp 218ꢂ219ꢀC; H NMR (400 MHz, DMSO-d6) dH: 5.79 (1H, s, ArCH),
7.01ꢂ8.73 (8H, m, ArH), 8.36 (1H, s, NH), 8.49 (1H, s, NH), 12.72 (1H, s, OH).
13C NMR (100 MHz, DMSO-d6) dC: 60.85, 111.89, 114.19, 123.90, 124.52, 128.68,
128.85, 130.09, 134.19, 135.00, 137.06, 146.95, 151.39, 165.89; MS (ESI): m=z
(%) ¼ 241.2 (100) [MþH]þ. IR (KBr): vmax 3428, 3083, 1671, 1611 cmꢁ1. Anal. Calcd.
for C14H12N2O2: C, 69.99; H, 5.03; N, 11.66. found: C, 69.59; H, 5.53; N, 11.03.
2-(4-Methoxyphenyl)-1,2-dihydroquinazolin-4(3H)-one (3j)
1
Mp 255–257ꢀC; H NMR (400 MHz, DMSO-d6) dH: 3.86 (3H, s, CH3), 5.67
(1H, s, CH), 6.42 (2H, dd, J ¼ 2.0, 7.6 Hz, ArH), 6.89–6.90 (1H, m, J ¼ 8.0 Hz,
ArH), 7.04 (1H, s, NH), 7.15 (1H, d, J ¼ 8.0 Hz, ArH), 7.20–7.21 (1H, m, J ¼ 8.0 Hz,
Hz, ArH), 7.36 (1H, dd, J ¼ 8.0 Hz, ArH), 7.45 (2H, dd, J ¼ 2.0, 7.6 Hz, ArH), 8.21
(1H, s, NH). 13C NMR (100 MHz, DMSO-d6) dC: 55.43, 65.36, 114.45, 114.71,
117.12 (2C), 117.69, 128.31 (2C), 128.75, 132.76, 133.79, 140.59, 147.56, 163.20;
MS (ESI): m=z (%) ¼ 255.1 (100) [M þ H]þ. IR (KBr): vmax 3269, 3171, 1678,
1602 cmꢁ1. Anal. calcd. for C15H14N2O2: C, 70.85; H, 5.55; N, 11.02. Found:
C, 70.88; H, 5.25; N, 10.81.
2-(4-Chlorophenyl)-1,2-dihydroquinazolin-4(3H)-one (3k)
1
Mp 227–228ꢀC; H NMR (400 MHz, DMSO-d6) dH: 5.78 (1H, s, CH), 6.67
(1H, t, J ¼ 8.0 Hz, ArH), 6.75 (1H, d, J ¼ 8.0 Hz, ArH), 7.15 (1H, s, NH),
7.25–7.27 (1H, m, J ¼ 8.0 Hz, ArH), 7.46–7.47 (2H, m, J ¼ 2.0, 6.4 Hz, ArH), 7.52
(2H, dd, J ¼ 2.0, 6.4 Hz, ArH), 7.62 (1H, dd, J ¼ 8.0 Hz, ArH), 8.34 (1H, s, NH).
13C NMR (100 MHz, DMSO-d6) dC: 65.79, 114.48, 114.97, 117.30, 127.39, 128.33,
128.34, 128.78 (2C), 132.99, 133.42, 140.70, 147.67, 163.50; MS (ESI): m=z
(%) ¼ 259.1 (100) [M þ H]þ. IR (KBr): vmax 3325, 3188, 1658, 1609, 1483 cmꢁ1. Anal.
calcd. for C14H11N2OCl: C, 65.00; H, 4.29; N, 10.83. Found: C, 65.38; H, 4.36;
N, 10.88.
2-(4-Chlorophenyl)-1,2-dihydroquinazolin-4(3H)-one (3l)
1
Mp 210–212ꢀC; H NMR (400 MHz, DMSO-d6) dH: 5.95 (1H, s, CH), 6.70
(1H, t, J ¼ 7.6 Hz, ArH), 6.79 (1H, d, J ¼ 8.0 Hz, ArH), 7.29 (1H, t, J ¼ 8.0 Hz,
ArH), 7.35 (1H, s, NH), 7.62 (1H, dd, J ¼ 7.6 Hz, ArH), 7.70 (1H, t, J ¼ 7.6 Hz,
ArH), 7.94 (1H, d, J ¼ 7.6 Hz, ArH), 8.21–8.22 (1H, m, J ¼ 1.4, 1.4 Hz, ArH), 8.36
(1H, t, J ¼ 1.8, 1.8 Hz, ArH), 8.53 (1H, s, NH). 13C NMR (100 MHz, DMSO-d6)

SYNTHESIS OF 1,2-DIHYDROQUINAZOLIN-4(3H)-ONES
639
dC: 65.20, 114.61, 114.97, 117.55, 121.59, 123.29, 127.43, 130.06, 133.39, 133.59,
144.32, 147.32, 147.73, 163.36; MS (ESI): m=z (%) ¼ 270.1 (100) [M þ H]þ; IR
(KBr): vmax 3296, 3188, 1653, 1610, 1532, 1353 cmꢁ1
C14H11N3O3: C, 62.45; H, 4.12; N, 15.61. Found: C, 62.16; H, 4.20; N, 15.24.
. Anal. calcd. for
2-(Furan-2-yl)-6-nitro-1,2-dihydroquinazolin-4(3H)-one (3m)
1
Mp 267ꢂ269ꢀC; H NMR (400 MHz, DMSO-d6) dH: 6.04 (1H, t, J ¼ 2.8 Hz,
CH), 6.37 (1H, d, J ¼ 2.8 Hz, FuH), 6.42–6.43 (1H, m, FuH), 6.86 (1H, d,
J ¼ 9.2 Hz, ArH), 7.65 (1H, s, NH), 8.12 (1H, dd, J ¼ 2.8, 9.2 Hz, ArH), 8.44
(1H, d, J ¼ 2.8 Hz, ArH), 8.65 (1H, s, NH), 8.83 (1H, d, J ¼ 1.6 Hz, FuH). 13C
NMR (100 MHz, DMSO-d6) dC: 60.58, 108.19, 111.17, 113.63, 115.15, 124.75,
129.57, 138.09, 144.05, 152.53, 154.19, 161.99; MS (ESI): m=z (%) ¼ 260.1 (100)
[MþH]þ; IR (KBr): vmax 3382, 3188, 3072, 1674, 1615, 1530, 1497, 1331, 1299,
1117 cmꢁ1. Anal. Calcd. for C12H9N3O4: C, 55.60; H, 3.50; N, 16.21. found: C,
55.74; H, 3.40; N, 16.15.
6-Nitro-2-(pyridin-4-yl)-1,2-dihydroquinazolin-4(3H)-one (3n)
1
Mp 231ꢂ234ꢀC; H NMR (400 MHz, DMSO-d6) dH: 6.38 (1H, t, J ¼ 2.8 Hz,
CH), 7.82 (1H, d, J ¼ 8.4 Hz, PyH), 7.95 (1H, s, NH), 8.01–8.04 (2H, m, PyH), 8.38
(1H, dd, J ¼ 2.4, 8.4 Hz, ArH), 8.68–8.71 (3H, ArH, PyH), 8.98 (1H, s, NH); 13C
NMR (100 MHz, DMSO-d6) dC: 61.52, 120.30(2C), 122.31, 122.53, 129.19, 130.08,
140.07, 145.89, 153.06(2C), 154.63, 162.15; MS (ESI): m=z (%) ¼ 271.1 (100)
[MþH]þ; IR (KBr): vmax 3340, 3183, 3072, 1679, 1619, 1567, 1466, 1347,
1143 cmꢁ1; Anal. Calcd. for C13H10N4O3: C, 57.78; H, 3.73; N, 20.73. found: C,
57.98; H, 3.40; N, 20.09.
ACKNOWLEDGMENTS
This work was supported by grants from both Beijing Municipal Commission
of Education and Beijing Institute of Technology. We are grateful for analytical
help from Beijing University Analysis Center and Institute of Chemistry, Chinese
Academy of Sciences.
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