Synthesis of some bisnitrosaccharins

Article abstract of DOI:10.1134/S1070427212100175

Method for synthesis of previously unknown bisnitrosaccharins from 6-nitrosaccharin under the action of bishalide compounds in polar aprotic solvents in the presence of anhydrous potassium carbonate is suggested. Pleiades Publishing, Ltd., 2012.

Full text of DOI:10.1134/S1070427212100175

ISSN 1070-4272, Russian Journal of Applied Chemistry, 2012, Vol. 85, No. 10, pp. 1581−1585. © Pleiades Publishing, Ltd., 2012.
Original Russian Text © B.A. Tagiev, G. Kazaz, B. Anyl, 2012, published in Zhurnal Prikladnoi Khimii, 2012, Vol. 85, No. 10, pp. 1648−1652.
ORGANIC SYNTHESIS
AND INDUSTRIAL ORGANIC CHEMISTRY
Synthesis of Some Bisnitrosaccharins
B. A. Tagieva,c, G. Kazazb, and B. Anylb
aChemical Department, Faculty of Natural Sciences and Literature, Kafkas University, Turkey
bChemical Department, Faculty of Natural Sciences and Literature, Ataturk University, Turkey
cInstitute of Polymeric Materials, National Academy of Sciences of Azerbaijan, Sumgaiyt, Azerbaijan
e-mail: babirtag@yahoo.com
Received June 10, 2011
Abstract—Method for synthesis of previously unknown bisnitrosaccharins from 6-nitrosaccharin under the action
of bishalide compounds in polar aprotic solvents in the presence of anhydrous potassium carbonate is suggested.
DOI: 10.1134/S1070427212100175
Aromatic polyimides containing phenyl oxide units
in the backbone are of great interest not only because
of their high thermal stability and flexibility, but also
owing to the improved solubility in readily available
organic solvents [1].
extensively studied polyimides, their sulfur-containing
analogs, i.e., polysaccharins, have been the subject of
only several reports [11–14]. The products synthesized
in these studied were for the most part difficultly soluble
and insufficiently macromolecular. In the present
communication, we suggest a method for synthesis of
previously unreported bisnitrosaccharins, which can be
used as monomers for synthesis of polyestersaccharines,
i.e., polysaccharine derivatives with improved
solubility. These bisnitrosaccharins were produced
by the nucleophilic substitution reaction between
nitrosaccharin and bishalide compounds in polar aprotic
solvents (PASs) in the presence of anhydrous K2CO3
(Scheme 1).
A method for synthesis of aromatic polyesterimides
via aromatic nucleophilic substitution of nitro groups
of bisnitrophthalimides with dianions of bisphenols has
been suggested [2].
It should b noted that the aromatic nucleophilic
substitution of the nitro group of nitrophthalimides with
the phenolate anion has been studied previously on
model reactions [3–5].
The nucleophilic substitution reaction between
activated aromatic imide-containing dinitro compounds
and dianions of bisphenols has also been used to
synthesize aromatic polyesterimides [6, 7]. It has been
shown that the reaction products have an improved
solubility in ordinary organic solvents and are easily
processed.
The structural formulas of compounds 3a–3c are
presented in Scheme 2.
Asthestartingproductforsynthesisof6-nitrosaccharin
served para-nitrotoluene. By successive treatment of this
compound with chlorosulfonic acid [15] and aqueous
ammonia [16], we obtained, respectively, sulfochloride
and sulfamide derivatives of para-nitrotoluene. Then,
the corresponding nitrosaccharin was produced from
the sulfamide derivative via oxidation by the known
methods [17, 18].
The introduction of phenyl oxide units into the
backbone of heterocyclic polymers has been used
to synthesize such derivatives as poly(aryl ether
phenylquinoxaline)s [8], poly(aryl ether phthalazine)
s [9], and poly(aryl ether phthalazinone)s [10], which
possess an improved solubility in ordinary organic
solvents.
Bisnitrosaccharins 3b, 3c were synthesized in
accordance with the above scheme. The reaction was
performed by heating of a mixture of stoichiometric
amounts of 6-nitrosaccharine (1) and the corresponding
bishalide compound 2a–2c in N,N-dimethylacetamide
It should be noted that, in contrast to the rather
1581

1582
TAGIEV et al.
Scheme 1.
K2CO3
PAS, Δ
2a–2c
1
3a–3c
where R =
X = Cl, Br.
b
a
c
Scheme 2.
3a
3b
3c
(DMAc) at 130°C for 3 h in the presence of anhydrous
K2CO3. The reaction products 3a–3c were obtained
in rather high yields (80–90%); on being purified by
recrystallization from DMFA, they had the form of
high-melting crystalline substances.
of the NO2 group, presumably overlaps the absorption
band of the >SO2 group. The absorption bands at 3100–
3000, 2930, and 2855 cm–1 can be attributed to aromatic
(=C–H) and aliphatic (–CH2) bonds, respectively. The
characteristic absorption bands observed in the IR
spectra of compounds 3a–3c are in good agreement with
published data [16, 19].
The composition and structure of the resulting
bisnitrosaccharins 3a–3c were characterized by
elemental analysis and IR and 1H NMR spectroscopies.
1
The H NMR spectra of bisnitrosaccharins 3a–3c
show signals with chemical shifts δ 7.35–9.40 ppm,
associated with the aromatic protons. In addition, the
signal observed at δ 1.22–5.08 ppm can be attributed
to the aliphatic ptrotons. These characteristic chemical
shifts are observed in the 1H NMR spectra of compounds
3a–3c (Figs. a–c).
The IR spectra of compounds 3a–3c contain
absorption bands at 1740, 1375–1270, and 1200–
1180 cm–1, characteristic of, respectively, the >C=O
and >SO2 groups of the saccharine ring. The absorption
band at 1540 cm–1 is characteristic of the NO2 group.
The absorption band at 1330 cm–1, also characteristic
RUSSIAN JOURNAL OF APPLIED CHEMISTRY Vol. 85 No. 10 2012

SYNTHESIS OF SOME BISNITROSACCHARINS
(a)
1583
(b)
(c)
δ, ppm
Fig. 1. 1H NMR spectra of compounds (a) 3a, (b) 3b, and (c) 3c in DMSO-d6. (δ) Chemical shift.
EXPERIMENTAL
except Na2CO3 from Merck): para-nitrotoluene,
chlorosulfonic acid, ammonia (24% aqueous
solution), 1,6-dibromohexane, α,α'-dichloro-para-
xylene, 4,4'-dichloromethylbiphenyl, K2Cr2O7, N,N-
The following starting products were used
in the study without additional purification (all
RUSSIAN JOURNAL OF APPLIED CHEMISTRY Vol. 85 No. 10 2012

1584
TAGIEV et al.
dimethylformamide, N,N-dimethylacetamide, K2CO3,
and Na2CO3 (Fluka).
9.80; S 11.20, 11.26. C22H14O10N4S2. Calculated (%):
С 41.27, Н 2.50, N 10.02, S 11.46. Н NMR spectrum
1
4-Nitrotoluene-2-sulfo chloride was synthesized by
the method previously described in the literature. The
product obtained in quantitative yield was used without
additional purification to synthesize the corresponding
sulfamide derivative.
(400 MHz, DMSO-d6), δ ppm): 9.40–9.20 s (Hс + Hс',
2Н), 8.71–8.70 d (J = 7.0 Hz, На+На', 2Н), 8.31–8.29
d (J = 7.0 Hz, Нb + Нb', 2Н), 7.42 s (2Hd + 2Hd', 4Н),
3.31 s (Нe + Не’, 4Н) (Fig. 1a).
N,N'-Biphenylene-4,4'-dimethylenebis(6-nitro-
saccharin) [N,N'-biphenylene-4,4'-dimethylenebis(6-
nitro-1,2-benzisothiazole-3-(2H)-OH-1,1-dioxide)]
(3b). Compound 3b was synthesized by the method
described for the case of compound 3a. The reaction of
compound 1 (10 mmol) with compound 2b (5 mmol)
in DMAc (35 mL) in the presence of anhydrous K2CO3
(5.2 mmol) yielded compound 3b. The yield of the
unpurified dry grayish-yellow solid product was 3.00 g
(94%), mp 314–316°C (with decomposition). On being
recrystallized from DMFA, compound 3b had the form
of grayish-yellow finely crystalline substance. Yield
2.62 g (80%), mp 322–324°C (with decomposition).
Found (%):С 52.64, 52.72; Н 2.74, 2.65; N 8.58,
8.65; S 10.38, 10.46. C28H18O10N4S2. Calculated (%):
4-Nitrotioluene-2-sulfamide was synthesized
from the corresponding sulfo chloride [16]. On being
recrystallized from water, the product had the form of
light gray fine needle-like crystals, yield 74%, mp 191–
192°C (published value 185–187°C [16]).
6-Nitrosaccharin
was
synthesized
from
4-nitrotoluene-2-sulfamide via oxidation by the known
methods [17, 18]. The yield of an unpurified dry solid
product was 90%. On being purified by precipitation
from an aqueous solution of Na2CO3,the product had
the form of a light yellow fine powder, yield 82%, mp
207–209°C (published value 209–211°C [16]).
N,N'-Xylinene-1,4-bis(6-nitrosaccharin) [N,N'-
xylinene-1,4-bis(6-nitro-1,2-benzisothiazole-3-
1
С 52.99, Н 2.88, N 8.82, S 10.10. Н NMR spectrum
(2H)-OH-1,1-dioxide)] (3a).
A
reaction vessel
(400 MHz, DMSO-d6), δ (ppm): 9.29–9.28 s (Hс+Hс',
2Н), 8.73–8.72 d (J = 1.8 Hz, На + На', 2Н), 8.33–8.31 d
(J = 1.8 Hz, Нb + Нb', 2Н), 7.66–7.64 d (J = 8.4 Hz,
2Нe + 2Не', 4Н), 7.50–7.25 d (J = 8.4 Hz, 2Hd+2Hd',
4Н), 4.99 s (2Hf + 2Hf', 4Н) (Fig. 1b).
equipped with a magnetic rabble, thermometer,
reflux condenser, and Dean–Stark apparatus was
charged with 11.40 g of compound (1) (50 mmol),
3.59 g of anhydrous K2CO3 (26 mmol), and 100 mL
of dimethylacetamide. The mixture was agitated for
15 min at room temperature,20 mL of toluene was
added, and the resulting mixture was heated on an oil
bath at 130°C until water release terminated. After water
was removed, 4.37 g of compound 2 (25 mmol) and
approximately 100 mg of KI were added to the reaction
mass. The reaction mixture was continued to be agitated
for 3 h at 130°C. In 20–25 min after the beginning of
the reaction, the reaction mixture turned dark brown
and remained so till the end of the reaction. After the
reaction was complete, the contents of the vessel were
cooled to room temperature and poured into 1 L of icy
water acidified with small amounts of hydrochloric
acid. The reaction product precipitated in the form of
beige floccules was collected, filtered off, washed on
the filter with water and then with a small amount of
methanol, and dried in air and then in a vacuum. The
yield of the unpurified solid product was 13.20 g (95%),
mp 314–316°C. On being recrystallized from DMFA,
product (3a) had the form of fine crystals with a light
straw color. Yield 12.50 g (90%), mp 334.6–335.2°C.
Found (%):С 46.85, 46.80; Н 2.30; 2.25; N 9.75,
N,N'-Hexamethylene-1,6-bis(6-nitrosaccharin)
[N,N'-hexamethylene-1,6-bis(6-nitro-1,2-benziso-
thiazole-3-(2H)-OH-1,1-dioxide)] (3c). Compound
3c was also synthesized by the method described for
synthesis of compound 3a, by the reaction of compound
1 (5 mmol) with compound 2c in DMAc (10 mL) in the
presence of anhydrous K2CO3 (2.6 mmol).The yield of
the unpurified dry product of light straw color was 1.27 g
(94%), mp 210–214°C. On being recrystallized from
DMFA1, compound 3c had the form of light yellow fine
crystals. Yield 1.16 g (86%), mp 242–244°C. Found (%):
С 44.34, 44.12; Н 3.18, 3.27; N 10.62, 10.70; S 12.32,
12.40. C20H18O10N4S2. Calculated (%): С 44.61, Н 3.37,
N 10.40, S 11.91.
1Н NMR spectrum (400 MHz, DMSO-d6), δ (ppm):
9.22–9.2 d (J = 1.8 Hz, Hс+Hс', 2Н), 8.70–8.69 d (J =
1.8 Hz, На + На', 2Н), 8.68–8.67 d (J = 1–8 Hz, Нb +
Нb', 2Н), 3.75–3.71 t (J = 6.9 Hz, 2Нe + 2Не', 4Н),
–––––––––––––––
1
The crystallization commenced upon addition of a small amount of
ethanol.
RUSSIAN JOURNAL OF APPLIED CHEMISTRY Vol. 85 No. 10 2012

SYNTHESIS OF SOME BISNITROSACCHARINS
1585
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CONCLUSIONS
Three bis(nitrosaccharin)s were synthesized for
the first time by the reaction of 6-nitrosaccharine
with bishalide compound and characterized: N,N '-
xylinene-1,4-bis(6-nitrosaccharin), N,N '-biphenylene-
4,4'-dimethylenebis(6-nitrosaccharin),
hexamethylene-1,6-bis(6-nitrosaccharin).
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Makromolecules, 2004, vol. 37, pp. 60–65.
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