One-pot synthesis and luminescent spectra of 3-allyl substituted quinazoline-2,4-dione derivatives as allyl capping agents

Article abstract of DOI:10.2478/s11696-011-0094-2

3-Nitro-N-(phenylsulphonyloxy)phthalimide (IIIa) and N-(phenylsulphonyloxy) phthalimide (IIIb) were synthesised as key intermediates in good yield. Their structures were confirmed by ¹H NMR and FTIR spectral data. The reaction of the key intermediates with allylamine produced 3-allyl-5- nitroquinazoline-2,4-(1H,3H)-dione (IVa) and 3-allylquinazoline-2,4-(1H,3H)- dione (IVb), respectively. Luminescence emission and excitation spectra of IVa and IVb are also presented.

Full text of DOI:10.2478/s11696-011-0094-2

Chemical Papers 66 (1) 75–78 (2012)
DOI: 10.2478/s11696-011-0094-2
SHORT COMMUNICATION
One-pot synthesis and luminescent spectra of 3-allyl substituted
quinazoline-2,4-dione derivatives as allyl capping agents
a,c
b
c
Mahmoud Farouk*, Salman A. Alrokayan, Ahamad Imran,
c
Khalid M. Abu-Salah
aFaculty of Science & Humanity Studies, Salman Bin Abdalaziz University, P. O. Box 83, Alkharj 11942, Saudi Arabia
bCentre of Excellence in Biotechnology Research, P. O. Box 2460, cKing Abdullah Institute for Nanotechnology,
P. O. Box 2454, King Saud University, Riyadh 11451, Saudi Arabia
Received 7 March 2011; Revised 5 August 2011; Accepted 6 August 2011
3
-Nitro-N-(phenylsulphonyloxy)phthalimide (IIIa) and N-(phenylsulphonyloxy)phthalimide (IIIb)
1
were synthesised as key intermediates in good yield. Their structures were confirmed by H NMR
and FTIR spectral data. The reaction of the key intermediates with allylamine produced 3-allyl-5-
nitroquinazoline-2,4-(1H,3H )-dione (IVa) and 3-allylquinazoline-2,4-(1H,3H )-dione (IVb), respec-
tively. Luminescence emission and excitation spectra of IVa and IVb are also presented.
ꢀ
c 2011 Institute of Chemistry, Slovak Academy of Sciences
Keywords: N-(phenylsulphonyloxy)phthalimides, 3-allylquinazoline-2,4-(1H,3H )-diones, lumines-
cence, allyl capping agent
The development of silicon nanoparticles (SiNPs)
functionalised with suitable organic molecules to pro-
duce surfaces with tailored optical and structural
properties has attracted a great deal of attention from
organic chemists and industrial researchers worldwide.
The photochemical stability of the functionalised sili-
con nanoparticles is a prime advantage for their use in
optoelectronic and biological applications (O’Farrell
et al., 2006). This could be achieved by tailoring the
silicon surfaces via the formation of thermodynami-
cally and kinetically stable covalent bonds (Si—C),
which involves the addition of silicon and hydrogen
to an unsaturated C—C bond (Buriak, 2002; Buriak
et al., 1999). Following these interesting applications,
the development of a new scaffold of 3-substituted
quinazoline-2,4-(1H,3H )-dione with allyl substituent
on N-3 atom has resulted from our programme for a
new organic tailor to de-activate the surface of SiNPs
as alkyl-capped oxide-free SiNPs (Farouk, 2009).
due to their diverse biological properties (Connolly et
al., 2005; Jain et al., 2008). Their structure can be
modified by substitution on N-1, C-5, and C-6 atoms
for further biological investigation. Various methods
of synthesis and reactants have been used to synthe-
sise these compounds (Connolly et al., 2005; Shiau et
al., 1990; Rivero et al., 2009). We used the reaction of
O-sulphonyl derivative of hydroxyamic acid (IIIa and
IIIb) with amine nucleophile under heating (Fahmy
et al., 1977, 1978; Fahmy, 2006), involving the Lossen
rearrangement (Sheradsky & Itzhak, 1986; G u¨ tschow,
1999) to afford the desired compounds IVa and IVb
(Fig. 1). Their application to the de-activation of ser-
ine proteases has been investigated previously (Neu-
mann & G u¨ tschow, 1994; Martyn et al., 1999; Kerri-
gan et al., 2000; Vagnoni et al., 2001). Here we de-
scribe the synthesis, chemical and photoluminescence
characterisation of compounds IVa and IVb suitable
as allyl capping agents to be used in the functionali-
sation of nanoparticles.
3
-Substituted quinazoline-2,4-(1H,3H )-diones rep-
resent a class of fused heterocyclic compounds (Ka-
tritzky & Rees, 1984) that are of considerable interest
3-Nitrophthalic anhydride and phthalic anhydride
were prepared following the described procedures (Vo-
*Corresponding author, e-mail: mfa23@yahoo.com

7
6
M. Farouk et al./Chemical Papers 66 (1) 75–78 (2012)
Fig. 1. Synthesis of 3-allylquinazoline-2,4-dione derivatives. Reaction conditions: i) NH2OH · HCl, pyridine, reflux, 30 min; ii)
◦
PhOSO2Cl, 0 C, diluted HCl; iii) allylamine, toluene, reflux, 3 h.
gel et al., 1989). Anhydrous solvents were dried fol-
lowing the standard procedures (Perrin & Armarego,
10.57; found: C, 55.48; H, 3.02; N, 4.66; S, 10.61.
3-Allyl-5-nitroquinazoline-2,4-(1H,3H )-dione(IVa)
was synthesised as follows: a mixture of phthalimide
derivative IIIa (0.70 mg, 2 mmol) and allylamine (0.2
mg, 2 mmol) in dry toluene (5 mL) was heated under
reflux for 3 h. The excess of allylamine was removed by
co-evaporation with toluene under reduced pressure.
The solid thus formed was dried and crystallised from
1
988).
Melting points were determined with a Thermo
Scientific Electrothermal IA9100 digital apparatus
Thermo Fisher Scientific Inc., USA) and are uncor-
(
rected. IR spectra were recorded on a Shimadzu 408
1
spectrometer using KBr pellet technique. H NMR
400 MHz) and 1 C NMR (100 MHz) spectra (in
3
◦
ethanol to afford IVa (0.36 mg, 72 %, m.p. of 170 C).
(
−
1
CDCl3 and DMSO-d6 using TMS as an internal stan-
dard) were recorded using Jeol Eclipse 400 spectrom-
eter. EI mass spectra were measured using Hewlett–
Packard (Agilent) 5988A GC/MS system at ionisation
energy of 70 eV. Luminescence emission and excitation
spectra were obtained with a Perkin–Elmer LS-55 flu-
orescence spectrometer using ethanol as a solvent and
a slit width of 10 nm.
IR (KBr), ν˜ /cm : 1346, 1533 (N—O), 1634–1659
(C—O), 2926 (C—H in CH2CH—CH2), 3076 (C—H
1
in benzene), 3250–3331 (NH). H NMR (DMSO-d6),
δ: 3.73 (t, 1H, J = 4.4 Hz, CH2CH—CH2), 3.90
(t, 1H, J = 5.5 Hz, CH2CH—CH2), 5.19 (m, 2H,
CH2CH—CH2), 5.86 (m, 1H, CH2CH—CH2), 7.54 (t,
1H, J = 8.9 Hz, Haryl), 7.71 (d, 1H, J = 8.1 Hz, Haryl),
7.94 (s, 1H, NH), 8.29 (d, 1H, J = 8.8 Hz, Haryl). 13
C
3
-Nitro-N-(phenylsulphonyloxy)phthalimide (III )
NMR (DMSO-d6), δ: 42.2 (C-9), 115.5 (C-4a), 116.5
(C-6), 117.8 (C-11), 123.3 (C-8), 135.0 (C-7), 136.3
(C-10), 138.8 (C-8a), 147.1 (C-5), 155.2 (C-2), 164.3
(C-4). For C11H9N3O4 (Mr = 247.06) wi/mass % cal-
culated: C, 53.44; H, 3.67; N, 17.00; found: C, 53.47;
H, 3.71; N, 17.04.
was prepared as follows: a mixture of nitrophthalic
anhydride (Ia) (3.0 g, 18.0 mmol), hydroxylamine hy-
drochloride (1.51 g, 23.3 mmol), and dry pyridine
5 mL) was heated under reflux for 30 min. Ben-
zenesulphonyl chloride (2.8 g, 15.9 mmol) was then
(
◦
added at −5 C and the reaction mixture was stirred
3-Allylquinazoline-2,4-(1H,3H )-dione (IVb) was ob-
◦
at this temperature for 15 min, followed by the ad-
dition of a cold HCl/H2O solution (ϕr = 1 : 1).
The precipitate thus formed was filtered, dried and
crystallised from toluene to afford IIIa (3.6 g, 67 %,
tained (0.34 mg, 85 %, m.p. of 176 C; Werbel (1967)
◦
reported m.p. of 182–185 C) following the above pro-
cedure and using phthalimide derivative IIIb (0.61 mg,
−
1
2 mmol) as a reactant. IR (KBr), ν˜ /cm : 1647–1659
(C—O), 2926 (C—H in CH2CH—CH2), 3068 (C—H
◦
m.p. of 178 C) as pale yellow crystals. IR (KBr),
−
1
1
1
ν˜ /cm : 1205 (SO2—O), 1750–1810 (C—O). H NMR
CDCl3), δ: 7.64 (t, 2H, J = 7.7 Hz, Haryl), 7.80 (t, 1H,
J = 7.3 Hz, Haryl), 8.01 (t, 1H, J = 7.7 Hz, Haryl), 8.15
m, 4H, Haryl). MS, m/z (Ir/%): 348 (46) (M ). For
C14H8N2O7S (Mr = 348.29) wi/mass % calculated:
C, 48.28; H, 2.31; N, 8.04; S, 9.20; found: C, 48.60; H,
.52; N, 8.34; S, 9.28.
N-(Phenylsulphonyloxy)phthalimide (IIIb) was ob-
tained (pale yellow crystals, 4.9 g, 80 %, m.p. of 170 C;
Buess and Bauer (1955) reported m.p. of 189–190 C)
following the above procedure and using phthalic an-
hydride (Ib) (3.0 g, 20.3 mmol) as a reactant. H NMR
CDCl3), δ: 7.62 (t, 1H, J = 7.8 Hz, Haryl), 7.81 (m,
H, ArH), 8.08 (d, 1H, J = 8.1 Hz, Haryl). MS, m/z
Ir/%): 303 (56) (M ). For C14H9NO5S (Mr = 303.02)
wi/mass % calculated: C, 55.44; H, 2.99; N, 4.62; S,
in benzene), 3128–3192 (NH). H NMR (CDCl3), δ:
(
4.70 (d, 2H, J = 5.9 Hz, CH2CH—CH2), 5.28 (m, 2H,
CH2CH—CH2), 5.96 (m, 1H, CH2CH—CH2), 7.19
(m, 2H, Haryl), 7.57 (m, 1H, Haryl), 8.11 (d, 1H,
J = 8.0 Hz, Haryl), 10.93 (s, 1H, NH). 13C NMR
(CDCl3), δ: 43.0 (C-9), 114.6 (C-8), 115.4 (C-11),
123.5 (C-4a), 128.4 (C-5), 131.6 (C-6), 131.9 (C-7),
135.1 (C-10), 138.8 (C-8a), 152.3 (C-2), 162.2 (C-4).
For C11H10N2O2 (Mr = 202.21) wi/mass % calculated:
C, 65.34; H, 4.98; N, 13.85; found: C, 66.39; H, 4.71;
N, 13.81.
The sequence of syntheses is shown in Fig. 1. Hy-
droxylamine hydrochloride was allowed to react with
anhydrides Ia or Ib in dry pyridine under reflux to give
the corresponding oxime IIa or IIb, respectively. These
were, without isolation, treated with benzenesulpho-
+
(
2
◦
◦
1
(
7
(
+

M. Farouk et al./Chemical Papers 66 (1) 75–78 (2012)
77
Fig. 2. Photoluminescence spectra of IVa (A) and IVb (B): Luminescence excitation (λex = 378 nm) (curve 1) and (λex = 255
nm, 292 nm, 328 nm) (curve 3); luminescence emission (λem = 438 nm) (curve 2) and (λem = 370 nm) (curves 4, 5, 6).
nyl chloride to give compounds IIIa and IIIb in 67 %
and 80 % yields, respectively. The IR spectra of IIIa
and IIIb showed the expected two bands correspond-
ing to the carbonyl groups of cyclic imides (Fahmy et
al., 1977, 1978; Fahmy, 2006; Fieser & Fieser, 1967).
The reaction of sulphonyloxy derivatives IIIa and
IIIb with allylamine afforded 3-substituted quinazo-
line-2,4-diones IVa and IVb in yields of 72 % and 85 %,
respectively. The presence of the nitro group may be
due to an initial attack of the amine on the carbonyl
in the ortho (not meta) position relative to the ni-
tro group in IIIa. Consequently, after ring opening,
the Lossen rearrangement would occur at the sub-
stituent in the meta position, thus leading to the 5-
nitro-substituted quinazolinedione IVa. The IR spec-
sults showed that the attachment of the electron-
withdrawing group (nitro group) at C-5 position in
IVa had no major effect on electronic spectra (λem =
438 nm) in comparison with compound IVb (λem =
370 nm).
To conclude, 3-allyl substituted quinazoline-2,4-
dione derivatives will provide the opportunity to de-
activate and tailor the nanoparticles with a thermo-
dynamically and kinetically stable organic capping
agent. These functionalised nanoparticles will then be
investigated in vivo.
Acknowledgements. This work was supported in part by the
Centre of Excellence in Biotechnology (Project No. CEBR-02)
and in part by the King Abdullah Institute for Nanotechnology
(Res. Project No. Nano 6/1429), King Saud University. We
−
1
also acknowledge the support of Faculty of Science & Humanity
Studies, Salman Bin Abdalaziz University.
trum of IVa revealed absorption bands at 1346 cm
−
1
and 1533 cm
corresponding to the N—O stretch-
−
1
ing vibrations. The absorption band at 2926 cm
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