Solvent-free synthesis of triazines using N-halosulfonamides

Article abstract of DOI:10.1039/c4ra10892b

In this study, N,N,N′,N′-tetrabromobenzene-1,3-disulfonamide and poly(N-bromo-N-ethylbenzene-1,3-disulfonamide) were used as efficient catalysts for the one-pot synthesis of 3,5,6-trisubstituted-1,2,4-triazines from readily available acid hydrazides, ammo

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Solvent-free Synthesis of Triazines Using N-Halosulfonamides
Ramin Ghorbani-Vaghei,*Azadeh Shahriari,a Zahra Salimi,a Somayeh Hajinazarib
Received (in XXX, XXX) Xth XXXXXXXXX 20XX, Accepted Xth XXXXXXXXX 20XX
DOI: 10.1039/b000000x
5
In this study, N,N,N',N'ꢀtetrabromobenzeneꢀ1,3ꢀdisulfonamide and poly(NꢀbromoꢀNꢀethylbenzeneꢀ1,3ꢀ
disulfonamide) were used as efficient catalysts for the oneꢀpot synthesis of 3,5,6ꢀtrisubstitutedꢀ1,2,4ꢀ
triazines from readily avalible acid hydrazides, ammonium acetate and dicarbonyl compounds at 100 °C
in good to excellent yields under solventꢀfree conditions.
1,2,4ꢀtriazine ring.19Thus a broad utility range has made triazines
Introduction
prime synthetic candidates thereby accentuating the need to
45 develop newer protocols for the synthesis of triazine derivatives
specially in solid phase because of their benefits such as moderate
reaction conditions, selectivity, easy work up, high yield and
reduction in waste.
10 A significant stratum of heterocycle that contains nitrogen is the
substituted triazine. The cycle of 1,2,4ꢀtriazine is an appropriate
synthetic platform to generate a wideꢀrange of the heterocycle
system via intramolecular DielsꢀAlder reaction.1ꢀ2
Results and Discussion
The variety of interesting properties provides numerous
15 applications for these compounds in medicine and agriculture.3ꢀ5
They have also been used in many pharmaceutical applications
such as hypertension and inhibition of platelets, metal ions and
dyes,6 antileukemic,7 potent neuroprotective agents,8 antiꢀ
inflammatory,9 antimalarial,10 antifungal,11 antibacterial,12
20 anticonvulsant13 and antiviral14 compounds. For example, some 7ꢀ
phenylimidazo[1,2ꢀb][1,2,4]triazine derivatives of the general
structure 1 (Fig. 1) have been developed as selective ligands for
50 To our interest in the application of N,N,N',N'ꢀ
tetrabromobenzeneꢀ1,3ꢀdisulfonamide [TBBDA] and poly(Nꢀ
bromoꢀNꢀethylbenzeneꢀ1,3ꢀdisulfonamide) [PBBS] (Fig. 2),20 in
organic synthesis,herein we introduce improved protocol for
preparation of aliphatic and aromatic 3,5,6ꢀtrisubstitutedꢀ1,2,4ꢀ
55 triazines, from the condensationof acid hydrazides, dicarbonyl
compounds, and ammonium acetate in the presence of TBBDA
and PBBS as catalysts at 100 ºC under solventꢀfree (Scheme 1).
γꢀaminobutyric acid type
A (GABAA) receptors and are,
therefore, of benefit in the treatment and prevention of adverse
25 conditions of the central nervous system (CNS).15 8ꢀ(4ꢀ
methoxyphenyl)ꢀ4ꢀoxoꢀ4,6,7,8ꢀtetrahydroimidazo[2,1ꢀc][1,2,4]ꢀ
triazineꢀ3ꢀcarbohydrazide (IMT) of the structure 2 (Fig.1) has
been detected as antioxidant and non selective antagonist of
adenosine A2A receptors.16 3ꢀhydrazinoꢀ5ꢀphenylꢀ1,2,4ꢀtriazines
30 of the general structure 3 (Fig. 1) have an antihypertensive
60 Fig. 2The structure of TBBDA and PBBS.
activity17
and
bisarylꢀ3ꢀ(pyridinꢀ2(4)ꢀyl)ꢀ1,2,4ꢀtriazine
derivatives of structure 4 (Fig. 1) use as a fluorescent sensor for
ferric salts.18
Scheme 1 Synthesis of multiꢀsubstituted triazine derivatives
65 It is easy to prepare TBBDA and PBBS being stable under
atmospheric conditions for two months. Furthermore, TBBDA
and PBBS are nonꢀvolatile, inexpensive, and safe catalysts. After
completion of the reaction, the catalysts are recovered and can be
reused for several times. Thus, after the production of the
70 trisubstituted triazines in the first run with TBBDA,which gave
the corresponding product in 80% isolated yield(Table 1, entry
5), the catalyst was subjected to a second reactionwhich gave the
product in 73% yield; the average chemical yieldfor four
consecutive runs was 48%.
35
Fig. 1 Some examples of triazine derivatives with different
properties
The main methods for producing substituted 1,2,4ꢀtriazine
include a series of reactions: semicarbazide, thiosemicarbazide or
40 aminoguanidine with 1,2ꢀdicarbonyl compounds or their
monoximes, with αꢀketo acids or their esters or amides, or with αꢀ
hydroxy ketones, all of which generate the NꢀNꢀCꢀN piece of the
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Also, TBBDA and PBBS are effective compared with some
other methods for triazine synthesis; for instance, improvement in
time of reaction and yield in 3,5,6ꢀtriphenylꢀ1,2,4ꢀtriazine(entry
14) from 4h /61% 21to 2.75h /90% (our research)or modification
of purification manner from column chromatography22to
purification with solvent (our research).
2
3
2.33/98
2/80
3.33/85
5
2.5/73
In recent years, the synthesis of compounds under solventꢀfree
reaction is an important task in heterocyclic synthesis. Therefore,
we decided to test this solventꢀfree reaction with various ratios of
10 catalysts and optimize the conditions for the formation of 1,2,4ꢀ
trisubstituted triazines using benzil, ammonium acetate and 3ꢀ
methoxybenzhydrazide (Table 1).
4
1.66/95
3.58/87
3/80
Table 1 Optimization of reaction conditions for the synthesis of
15 trisubstituted 1,2,4ꢀtriazinesa
5
6
4.41/72
5.33/85
80/73/65
/48
[TBBDA(1ꢀ
10) PBBS (11ꢀ
15) (g)]
Entry
Solvent
Temperature Time Yield
(˚C)
(h)
(%)
3/98
Me
Me
1
2
3
4
5
6
7
8
9
Solventꢀfree
Solventꢀfree
Solventꢀfree
Solventꢀfree
Solventꢀfree
Solventꢀfree
Solventꢀfree
Solventꢀfree
Ethanol
0
100
100
100
100
100
100
80
2
3.5
3.40
3.35
3.15
3
trace
48
65
87
60
60
55
87
ꢀ
N
N
N
0.02
0.04
0.06
0.08
0.1
7
8
1.75/75
4/60
3/87
9.5/72
0.06
0.06
0.06
4.15
3
110
100
5
10
11
12
14
15
Ethanolꢀwater
Solventꢀfree
Solventꢀfree
Solventꢀfree
Solventꢀfree
0.0.6
0.0.6
0.08
0.1
110
100
100
100
100
5
ꢀ
9
1.33/88
6/68
5
64
68
72
72
4.41
4.41
4.41
0.12
10
11
12
1.41/80
2.08/75
2.5/65
3.66/65
4/60
aExperimental conditions: benzil (1 mmol), ammonium acetate (5 mmol)
and 3ꢀmethoxybenzhydrazide (1 mmol)
Table
2 Synthesis of various trisubstituted triazinesusing
TBBDA and PBBS as catalysts
20
Time (h)/yieldb(%)
Entry
Substrate
Substrate
Producta
TBBDA
PBBS
4.33/60
1
1.66/70
3.75/65
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Acknowledgements
We would like to thank BuꢀAli Sina University, Center of
Excellence in Developmental of Environmentally Friendly
35 Methods for Chemical Synthesis (CEDEFMCS) for financial
support of this study.
3.41/84
13
1.33/95
2.75/90
Notes and references
aDepartment of Organic Chemistry, Faculty of Chemistry, Bu-Ali Sina
University,65174, Hamedan, Iran Fax/Tel +98(81)38257407; E-mail:
40 rgvaghei@yahoo.com
† Materials and Equipment
All commercially available chemicals were obtained from Merck Fluka
and Aldrich companies, and were used without further purification unless
otherwise stated. Nuclear magnetic resonance 1H and 13CNMR spectra
45 were recorded on Bruker Avance 400 MHz FT NMR spectrometers
(undertaken at University of Mazandaran and University of Kashan, Iran).
Infrared (IR) spectroscopy was conducted on a Perkin Elmer GX FTꢀIR
spectrometer. Mass spectra were recorded on a Shimadzu QP 1100 BX
Mass Spectrometer (University of Tehran, Iran). Elemental analyses
14
3.83/86
aThe known compounds were characterized from their physical
properties, in comparison with authentic samples, and by spectroscopic
methods.
bIsolated yield.
50 (C,H,N) were performed with
(University of Tehran, Iran).
Typical procedure for the preparation of 3ꢀ(3ꢀmethoxyphenyl)ꢀ5,6ꢀ
diphenylꢀ1,2,4ꢀtriazine(Table 2, entry 5)
a Heraeus CHNꢀOꢀRapid analyzer
5
The probable mechanism of these catalysts is based on releasing
Br+in situ, which can act as an electrophilic species.23ꢀ27
Therefore, the mechanism shown in Scheme 2 may be suggested
for the conversion of the various doctrines, acid hydrazides and
In a round flask mixture of benzil (0.21 g, 1 mmol) and TBBDA (0.06 g,
55 0.11 mmol ) or PBBS (0.1 g) was heated at 100 °C. After 3 min 3ꢀ
methoxy benzhydrazide (0.16 g, 1 mmol) and ammonium acetate (0.38 g,
5 mmol) were added to the mixture and stirred for appropriate time (Table
2, entry 5). After completion of the reaction [TLC acetone/nꢀ
hexane/toluene (3:20:4)],CH2Cl2 (10 mL) was added (TBBDA was
60 precipitated and the catalyst was removed by filtration).Then reaction
filtered and washed with ether (3×15 mL) and it was rinsed with water.
The crude product was recrystallized from ethanol, the pure product (0.29
g, 87%) was obtained as a yellow powder. Mp: 133ꢀ135 °C;IR (KBr):
3066, 3004, 2945, 1607, 1582, 1499, 690;1H NMR (400 MHz, CDCl3): δH
65 (ppm) 3.95 (s, OCH3, 3H), 6.89ꢀ8.25 (m, CH aromatic, 14H). 13C NMR
(100 MHz, CDCl3): δc (ppm) 55.50, 112.79, 118.08, 120.92, 128.53,
128.62, 129.47, 129.60, 129.89, 130.73, 135.51, 135.86, 136.15, 155.52,
155.57, 160.07, 161.06. MS: m/z 340, Anal. Calcd for C22H17N3O: C,
77.86; H, 5.05; N, 12.38; Found: C, 78,55; H, 5.18; N, 12.54.
28ꢀ29
ammonium acetate to trisubstituted triazines.
Initially, the
10 reaction involves a Br+ transfer from the catalysts to diketone to
form (A), then nucleophilic attack of acid hydrazide to A
produced (B). After the reaction of B with ammonium acetate
followed by intramolcular cyclization and elimination of H2O,
1,2,4ꢀtriazine derivatives (D) are obtained.
15
70
3ꢀ(3ꢀMethoxyphenyl)ꢀ5,6ꢀdi(pꢀtolyl)ꢀ1,2,4ꢀtriazine (Table 2, entry 1):
Yellow powder. Mp: 100ꢀ103 °C (99°C)30; 1H NMR (400 MHz CDCl3):
δH (ppm) 2.41 (s, CH3, 3H), 2.42 (s, CH3, 3H), 3.95 (s, CH3, 3H), 7.11ꢀ
8.28 (m, CH aromatic, 12H). 13C NMR (100 MHz, CDCl3): δc (ppm)
75 21.43, 21.52, 55.49, 112.67, 117.93, 120.84, 129.25, 129.30, 129.33,
129.81, 132.80, 133.13, 136.33, 139.67, 141.17, 155.32, 155.41, 160.02,
160.75. MS: m/z 367. . Anal. Calcd for C24H21N3O: C, 78.45; H, 5.76; N,
11.44; Found: C, 77.43; H, 5.83; N, 11.09.
80 5,6ꢀBis(4ꢀmethoxyphenyl)ꢀ3ꢀphenylꢀ1,2,4ꢀtriazine(Table 2, entry 2):
Yellow powder. Mp: 155ꢀ158 °C (165 °C)30; IR (KBr): 2967, 2938, 2842,
1605, 1574, 1488, 1254; 1H NMR (400 MHz CDCl3): δH (ppm) 3.87 (s,
OCH3, 3H), 3.88 (s, OCH3, 3H), 6.90ꢀ8.68 (m, CH aromatic, 13H).13C
NMR (100 MHz, CDCl3): δc (ppm) 55.34, 55.40, 113.99, 114.12, 128.19,
85 128.23, 128.76, 130.76, 131.30, 131.54, 135.04, 154.58, 154.76, 160.67,
160.70, 161.74. MS: m/z 369. Anal. Calcd for C23H19N3O2 C, 74.78; H,
5.18; N, 11.37; Found: C, 74.77; H, 4.87; N, 11.09.
20
Scheme 2 Suggested mechanism for the synthesis of substituted
triazines
25
3ꢀMethylphenanthro[9,10ꢀe][1,2,4] triazine (Table 2, entry 3): Yellow
90 powder. Mp: 166ꢀ168 °C; IR (KBr): 3117, 3065, 1699, 1672, 1185, 948;
1H NMR (400 MHz, CDCl3): δH (ppm) 2.54 (s, CH3, 3H), 7.28ꢀ8.34 (m,
Conclusions
CH
aromatic,
8H)
13C
NMR
(100
In this study, we have developed an efficient procedure for the
synthesis of 1,2,4ꢀ triazine derivatives using [TBBDA] and
[PBBS] as new catalysts. This method offers several advantages
30 such as being inexpensive catalysts, easy synthetic procedure,
good to high yields and an easy isolation.
MHz,CDCl3):δc(ppm)19.93,123.01,123.13,124.2,128.06,128.83,129.15,12
9.35,130.09,130.82,131.67,134.98,136.38,175.09.MS: m/z 245.
95
5,6ꢀBis(4ꢀmethoxyphenyl)ꢀ3ꢀ(pꢀtolyl)ꢀ1,2,4ꢀtriazine (Table 2, entry 4):
Yellow powder. Mp: 146ꢀ148 °C (149°C)30; IR (KBr): 3042, 3014, 2961,
2839, 1606, 1577, 1484, 1177, 832 ; 1H NMR (400 MHz, CDCl3): δH
(ppm) 2.47 (s, CH3, 3H), 3.86 (s, OCH3, 3H), 3.86 (s, OCH3, 3H), 6.89ꢀ
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8.56 (m, CH aromatic, 12H).13C NMR (100 MHz, CDCl3): δc (ppm)
55.33, 55.38, 113.95, 114.08, 128.15, 128.28, 128.32, 129.54, 130.73,
131.53, 132.30, 154.50, 154.53, 160.63, 160.73, 161.67. MS: m/z 383.
5. H. Neunhoeffer, Comprehensive Heterocyclic Chemistry, Katritzky A
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J Med Chem. 1991, 26, 179.
75
5
5,6ꢀBis(4ꢀmethoxyphenyl)ꢀ3ꢀmethylꢀ1,2,4ꢀtriazine (Table 2, entry 6):
Yellow powder. Mp: 122ꢀ125 °C (109ꢀ113 °C)31; IR (KBr): 2932, 2838,
1607, 1577, 1255, 832; 1H NMR (90 MHz, DMSOꢀd6): δH (ppm) 2.81 (s,
CH3, 3H), 3.34 (s, OCH3, 6H), 6.936ꢀ7.450 (m, CH aromatic, 8H). MS:
m/z 307.
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80 9. Z. K. Abd ElꢀSamii, J.Chem. Tech. Biotech. 1992, 53, 143.
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10
3ꢀPhenylꢀ5,6ꢀdi(pꢀtolyl)ꢀ1,2,4ꢀtriazine (Table 2, entry 7): Yellow powder.
Mp: 165ꢀ166 °C (168 °C)30; IR (KBr): 3062, 3032, 1608, 1490, 1366,
1
697; H NMR (400 MHz, CDCl3): δH (ppm) 2.42 (s, CH3, 3H), 2.42 (s,
CH3, 3H), 7.19ꢀ8.69 (m, CH aromatic, 13H). 13C NMR (100 MHz, 85 12. K. Srinivas, U. Srinivas, V. J. Rao, K. Bhanuprakash, K. H. Kishore,
15 CDCl3): δc (ppm) 21.43, 21.52, 128.27, 128.78, 129.25, 129.30, 129.33,
129.80, 131.39, 132.83, 133.182, 134.96, 139.64, 141.14, 155.31, 155.38,
160.96. MS: m/z 337.Anal. Calcd for C23H19N3: C, 81.87; H, 5.68; N,
12.45 Found: C, 83.07; H, 5.78; N, 12.44.
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90
95
20 5,6ꢀDimethylꢀ3ꢀ(pyridinꢀ4ꢀyl)ꢀ1,2,4ꢀtriazine (Table 2, entry 8): Yellowish
powder. Mp: 119ꢀ121 °C; IR (KBr): 2957, 2925, 2855, 1597, 1518, 1397,
1
1384, 783; H NMR (400 MHz, DMSOꢀd6): δH (ppm) 2.61 (s, CH3, 3H),
2.68 (s, CH3, 3H), 8.26ꢀ8.80 (m, CH aromatic, 4H). 13C NMR (100 MHz,
DMSOꢀd6): δc (ppm) 19.76, 22.24, 121.60, 142.68, 151.12, 158.50,
25 159.80, 160.686.MS: m/z 186.
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5,6ꢀDiphenylꢀ3ꢀ(pyridinꢀ4ꢀyl)ꢀ1,2,4ꢀtriazine (Table 2, entry 9): Yellow
powder. Mp: 163ꢀ164 °C;1H NMR (400 MHz CDCl3): δH (ppm) 7.28ꢀ8.87
18. P. Thirumurugan, P. T. Perumal, Dyes and Pigments. 2011, 88, 403.
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(m, CH aromatic, 14H).13C NMR (100 MHz, CDCl3): δc (ppm) 121.87, 100
30 128.68, 128.75, 129.52, 129.87, 130.02, 131.11, 135,07, 135.32, 142.19,
150.76, 155.95, 156.74, 159.64. MS: m/z 310. Anal. Calcd for C20H14N4:
C, 77.40; H, 4.55; N, 18.05 Found: C, 77.48; H, 4.33; N, 17.71.
22.H. A. Saad, M. M. Yousef, M. A. Mosselhi.Molecules 2011, 16, 4937.
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35 10): Yellow powder. Mp: 155ꢀ157 °C; IR (KBr): 3071, 3034, 2936, 2839,
1603, 1576, 1485, 1257, 828; H NMR (400 MHz, DMSOꢀd6): δH (ppm)
3.80 (s, OCH3, 3H), 3.81 (s, OCH3, 3H), 6.98ꢀ8.86 (m, CH aromatic,
12CH). 13C NMR (100 MHz, DMSOꢀd6): δc (ppm) 55.74, 55.87, 114.54,
114.62, 121.84, 127.75, 128.05, 131.19, 132.00, 142.46, 151.21, 155.37, 110
40 156.47, 158.91, 160.92, 161.99.MS: m/z 370.
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1
3,5,6ꢀTri(pꢀtolyl)ꢀ1,2,4ꢀtriazine(Table 2, entry 11): Yellow powder.Mp:
166ꢀ167 °C (165 °C)30; IR (KBr): 3031, 2918, 2863, 1610, 1490, 819.55;
1H NMR (400 MHz CDCl3): δH (ppm) 2.41 (s, CH3, 3H), 2.41 (s, CH3, 115 28. R. GhorbaniꢀVaghei, H. Shahbazi, C. R. Chimie. 2013, 16 , 1047.
45 3H), 2.48 (s, CH3, 3H), 7.19ꢀ8.58 (m, CH aromatic, 12H). 13C NMR (100
MHz, CDCl3): δc (ppm) 21.43, 21.52, 21.64, 128.23, 129.23, 129.28,
129.30, 129.56, 129.79, 132.22, 132.93, 133.28, 139.52, 141.04, 141.79,
155.13, 155.24, 161.03. MS: m/z 351.
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Commun. 2007, 37, 261.
120 31. E. Lilly, Chem.Abstr,.1980, 85, 33089.
50 3ꢀ(Pyridinꢀ4ꢀyl)ꢀ5,6ꢀdi(pꢀtolyl)ꢀ1,2,4ꢀtriazine (Table 2, entry 12): Yellow
powder. Mp: 145ꢀ147 °C; IR (KBr):3066, 3031, 2979, 1608, 1492, 1390,
697; 1H NMR (400 MHz CDCl3): δH (ppm) 2.42 (s, CH3, 6H), 7.20ꢀ8.86
(m, CH aromatic, 12H).13C NMR (100 MHz, CDCl3): δc (ppm) 21.46,
21.54, 121.81, 129.35, 129.39, 129.46, 129.80, 132.37, 132.61, 140.19,
55 141.65, 142.38, 150.69, 155.71, 156.55, 159.30.MS: m/z 338.
3ꢀ(3ꢀMethoxyphenyl)ꢀ5,6ꢀbis(4ꢀmethoxyphenyl)ꢀ1,2,4ꢀtriazine (Table 2,
entry 13): Yellow powder. Mp: 139ꢀ140 °C; IR (KBr):3070, 2936, 2836,
1604, 1579, 1498, 1255, 1175; 1H NMR (400 MHz CDCl3): δH (ppm) 3.86
60 (s, OCH3, 3H), 3.86 (s, OCH3, 3H), 3.94 (s, OCH3, 3H), 6.89ꢀ8.25 (m,CH
aromatic,12H). 13C NMR (100 MHz, CDCl3): δc (ppm) 55.33, 55.39,
55.48, 112.64, 113.98, 114.11, 117.79, 120.75, 128.14, 128.18, 129.80,
130.75, 131.54, 136.42, 154.57, 154.80, 160.01, 160.45, 160.72, 161.75.
MS: m/z 399.
65
References
1. D. L. Boger, Chem Rev. 1986, 86, 781.
2. S. C. Benson, J. H. Li, J. K. Snyder, J. Org .Chem. 1992, 57, 5285.
70 3. D. L. Boger, Tetrahedron 1983, 39, 2869.
4. W. A. Romanchik, M. M. Joullie, Heterocycles 1978, 9, 1631.
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