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Synthesis of 1,3,5-Triazines in Solvent-Free Conditions Catalysed by Silica

Supported Lewis Acid

Article  in  Green Chemistry · August 2002

DOI: 10.1039/b202014a

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Synthesis of 1,3,5-triazines in solvent-free conditions catalysed
by silica-supported lewis acids

Angel Díaz-Ortiz, Antonio de la Hoz,* Andrés Moreno, Ana Sánchez-Migallón and

Gema Valiente

Area de Química Orgánica, Facultad de Química, Universidad de Castilla-la Mancha,

E-13071 Ciudad Real, Spain. E-mail: antonio.hoz@uclm.es

Received 26th February 2002

First published as an Advance Article on the web 18th June 2002

The preparation of symmetrically substituted 1,3,5-triazines has been performed by cyclotrimerization of nitriles in
solvent-free conditions using silica-supported Lewis acids as catalysts. Although microwave irradiation gives the
best overall results in a short time, the best yields were obtained by conventional heating over periods of 24 h.
The use of these recyclable and environmentally benign catalysts produces yields similar to those obtained with
the more complex and contaminant lanthanide catalysts. This fact, together with the use of solvent-free conditions,
makes this procedure an environmentally benign synthetic method.

Introduction mainly of a dispersion of small particles of ZnCl2 on the surface

Supramolecular chemistry has been described as ‘chemistry
beyond the molecule’, and the goal in this area is to gain control
over the intermolecular non-covalent bond.1 The principal
characteristic of supramolecular chemistry is that building
blocks are reversibly linked through intermolecular forces. Due
to their characteristic C3-symmetry, 1,3,5-triazines have been
used in multidimensional crystal engineering using halo-
gen…p-interactions,2 and also in multidimensional crystal
engineering involving metal complexes that,3 in some cases,
produce nanometer-sized oligonuclear coordination com-
pounds.4
1,3,5-Triazines have also been used as templates in the
synthesis of supramolecular porphyrin systems,5 as complexa-
tion agents in analytical chemistry,6 as multi-step redox
systems,7 as stationary phases in HPLC resolution of racemic
compounds,8 as enantio-differentiating coupling reagents9 and
as high-loading scavenger resins for combinatorial chem-
istry.10
The synthesis of 1,3,5-triazines has been performed by
cyclotrimerization of nitriles catalysed by acids, bases11 or
activated magnesium.12 These reactions require strong reaction
conditions, i.e. high temperatures, pressures and long reaction
times, and give, in most cases, moderate yields. Alternatively,
the use of very strong and highly polluting acids11f or metals12
can be considered.
Green or sustainable chemistry is the design, development,
and implementation of chemical products and processes aimed
at reducing or eliminating the use and generation of substances
hazardous to human health and the environment.13 Among the
twelve principles of green chemistry, the use of heterogeneous
catalysis is one of the keystones of this new concept.13
Supported reagents have become of increased interest in the
fields of organic and organometallic synthesis. In this respect,
heterogeneous reactions in the presence of organic solvents
have been performed with great success.14 However, an even
more green alternative is the use of supported reagents in
solvent-free conditions.
Heterogeneous catalysts such as ZnCl2, TiCl4 and Et2AlCl
supported on silica gel have shown great utility as Lewis acid
catalysts. The structures of these systems are not known in great
detail but it is considered that silica-supported ZnCl2 consists
of silica gel. On the other hand, treatment of silica gel with TiCl4
and Et2AlCl results in the displacement of two chloride or ethyl
groups, respectively, by the silanol groups of the silica gel
(Scheme 1).15
These catalysts can be stored and recovered after the reaction
without loss of catalytic activity. In this regard these catalysts
have been used in the cycloaddition of furan with several
dienophiles,16 as well as in the preparation of amino acid
derivatives by amidoalkylation of heterocyclic compounds.17
Microwave irradiation has shown its utility in many organic
reactions. Spectacular accelerations have been observed in
numerous cases but, more importantly, the selectivity of many
reactions can be modified using microwaves and some reactions
that do not occur, or result in very low yields, can be improved
using microwaves.18 Reactions that require harsh conditions,
long reaction times, high temperatures and pressures—partic-
Scheme 1
Green Context
The synthesis of symmetrical 1,3,5-triazines is an important
transformation and is often carried out by the displacement
of chloride from cyanuric chloride, a wasteful method which
may be tricky to drive to completion. Here, the use of silica
supported Lewis acids and a basic promoter allows the
smooth and high yielding synthesis of such molecules in the
absence of solvent. Some side reactions are seen (SNAr2 and
demethylation of methoxyaromatics)—these may also be of
interest in different applications. DJM

DOI: 10.1039/b202014a Green Chemistry, 2002, 4, 339–343 339

This journal is © The Royal Society of Chemistry 2002
ularly when sensitive compounds are involved—are the best
candidates for improvement using microwaves.

Results and discussion

In this paper we describe the cyclotrimerization of nitriles to
afford 1,3,5-triazines in solvent-free conditions using silica-
supported ZnCl2, AlCl3 and TiCl4 as catalysts. These systems
represent a green alternative to the use of lanthanide ions. For
the sake of comparison, we also studied the commonly used
lanthanide catalyst yttrium trifluorosulfonate Y(OTf)3. Piper-
idine and morpholine were used as nucleophiles to induce the
cyclotrimerization. We used conventional heating and micro-
wave irradiation as the energy sources and the reactions were Scheme 2
performed under pressure in closed vessels.
The best results from these reactions are collected in Table
1.
Reactions under microwave irradiation conditions give the
best results in conjunction with short reaction times. However,
when the reaction time was increased to 24 h under conven-
tional heating the yields were greatly improved in most cases.
Such extended reaction times cannot be employed with
microwaves.
The results obtained are slightly better when Y(OTf)3 was
used instead of the silica-supported Lewis acids, although the
simple manipulation, possible re-utilization and known envi-
ronmental advantages make the silica systems excellent cata-
lysts for the cyclotrimerization of nitriles. As has been Scheme 3
previously described these catalysts can be recovered and stored
up to one month, which give rise to high conversions without
loss of catalytic activity.15
It can be seen from the results that, of the modified silica gels,
Si(Zn) gives the best results. This fact has been explained in
terms of the Hard–Soft Acid–Base Principle (HSAB): Zn,
which is softer than Al and Ti, coordinates more effectively with
the soft N atom of the nitrile. The only exceptions to this rule is
derivative 8, where the presence of a second coordinative
nitrogen in the pyrazole makes Si(Ti) the best catalyst.
In some examples the nitriles do not produce the expected
triazine. For example, the reaction with p-methoxybenzonitrile
(5) produced p-hydroxybenzonitrile by nucleophilic attack at
the methyl group of the anisole, which is activated by the Lewis Scheme 4
acid (Scheme 2).
The reaction involving p-chlorobenzonitrile (6) led to
aromatic nucleophilic substitution of the chlorine by both
piperidine and morpholine to give 18 and 19, together with the
amidines 20 and 21, respectively, which are intermediates in the
cyclization to the triazine (Schemes 3 and 4).11e
The substitution product 19 afforded the corresponding
triazine 14 in low yield together with the corresponding amidine
22 (Scheme 5).
In conclusion, silica gels modified with Lewis acids,
especially with ZnCl2, are effective catalysts for the cyclo-
trimerization of aliphatic and aromatic nitriles to 1,3,5-triazines.
The use of reagents supported on silica gel and the absence of
solvents means that this process can be classified as an
environmentally benign procedure.

Experimental
Silica-supported catalysts Si(Zn), Si(Al) and Si(Ti) were
prepared from silica gel and ZnCl2, AlEt2Cl and TiCl4,
respectively, according to known procedures.15 The resulting
catalysts were stored under argon. Si(Zn) was activated by
heating at 150 °C for 2 h under vacuum while Si(Al) and Si(Ti)
were used without prior activation. Scheme 5

340 Green Chemistry, 2002, 4, 339–343

Table 1 Cyclotrimerization of nitriles in solvent-free conditions

Starting material Catalyst Reaction conditions Product Yield (%)

Y(OTf)3 200 °C, 24 h 84

Y(OTf)3 160 °C, 210 W, 1 h 37
Si(Zn) 200 °C, 24 h 60
Si(Zn) 200 °C, 210 W, 2 min, 120 W, 28 min 50
Si(Al) 200 °C, 24 h 22
Si(Al) 200 °C, 210 W, 2 min, 120 W, 28 min 37
Si(Ti) 20 °C, 24 h 38
Si(Ti) 200 °C, 210 W, 2 min, 120 W, 28 min 37

Y(OTf)3 200 °C, 24 h 31

Y(OTf)3 160 °C, 210 W, 2 min, 150 W, 28 min 40
Si(Zn) 200 °C, 24 h 75
Si(Zn) 160 °C, 210 W, 2 min, 150 W, 28 min 35
Si(Al) 20 °C, 24 h 72
Si(Al) 115 °C, 210 W, 2 min, 150 W, 28 min 5
Si(Ti) 200 °C, 24 h 63
Si(Ti) 120 °C, 210 W, 2 min, 150 W, 28 min 0

Y(OTf)3 20 °C, 24 h 55
Y(OTf)3 140 °C, 210 W, 2 min, 45 W, 58 min 0
Si(Zn) 200 °C, 24 h 13
Si(Zn) 16 °C, 270 W, 1 h 0

Y(OTf)3 200 °C, 12 h 42

Si(Zn) 200 °C, 24 h 35
Si(Al) 200 °C, 24 h 6
Si(Ti) 200 °C, 24 h 5

Y(OTf)3 200 °C, 24 h 54

Y(OTf)3 160 °C, 210 W, 9 min, 120 W, 51 min 95
Si(Zn) 200 °C, 24 h 46

Y(OTf)3 200 °C, 24 h 27a

Y(OTf)3 200 °C, 24 h 72b

Y(OTf)3 200 °C, 24 h 60c

Y(OTf)3 200 °C, 24 h 30

Si(Zn) 200 °C, 24 h 30
Si(Al) 200 °C, 24 h 0
Si(Ti) 200 °C, 24 h 8

Y(OTf)3 200 °C, 24 h 66

Si(Zn) 200 °C, 24 h 15
Si(Al) 200 °C, 24 h 39
Si(Ti) 200 °C, 24 h 50

a 20 (9%). b Piperidine, 2 equiv., 20 (5%). c Morpholine, 2 equiv., 21 (6%).

Green Chemistry, 2002, 4, 339–343 341

 2,4,6-Triphenyl-1,3,5-triazine (11),19 cyanopyrazoles 7 and 8
and the corresponding triazines 15 and 1611b have been
described previously.
Synthesis of nitriles
p-Piperidinobenzonitrile (18). Yttrium trifluoromethane-
sulfonate (0.1 mmol, 0.08 g), p-chlorobenzonitrile (10 mmol,
1.37 g) and anhydrous piperidine (20 mmol, 2 ml) were heated
under argon in a screw-cap sealed reaction vessel in an
aluminium block20 at 200 °C for 24 h. The crude product was
extracted with acetone (2 3 10 ml) and filtered. The filtrate was
purified by column chromatography on silica gel using hexane–
ethyl acetate 9+1 as the eluent. p-piperidinobenzonitrile (18)
(1.34 g, 72%) eluted first followed by piperidino-p-chloro-
benzamidine (20) (0.2 g, 5%).
p-Piperidinobenzonitrile (18). Mp 55–57 °C (hexane–ethyl
acetate). 1H NMR (300 MHz, CDCl3, TMS as internal ref.) d
1.65–1.67 (m, 6H, H3,4,5), 3.33 (m, 4H, H2,6), 6.80–6.88 and
7.43–7.50 (4H, aryl). 13C NMR (300 MHz, CDCl3, TMS as
internal ref.) d 24.23 (piperidine C4), 25.23 (piperidine C3,5),
48.41 (piperidine C2,6), 98.93 (C1), 114.02 (C3,5), 120.32 (CN),
133.45 (C2,6), 153.54 (C4). IR (KBr) n(cm21): 2215 (nC·N),
1605, 1514 (nCNC). Analysis: Calc. for C12H14N2: C 77.38, H
7.58, N 15.04. Found: C 77.30, H 7.60, N 15.41%. MS (EI): m/z
185 (M 2 1).
Piperidino-p-chlorobenzamidine (20). Mp 64–65.7 °C (hex-
ane–ethyl acetate). 1H NMR (300 MHz, DMSO, TMS as
internal ref.) d 1.35–1.65 (m, 10H, piperidine), 7.37 and 7.48
(4H, JAX 8 Hz, JAAA 4.4 Hz, JAXA 0.3 Hz, aryl). 13C NMR (300
MHz, DMSO, TMS as internal ref.) d 24.00 (piperidine C4),
25.21 (piperidine C3), 25.91 (piperidine C5), 42.35 (piperidine
C2), 48.00 (piperidine C6), 128.47 (aryl C2,6), 128.62 (aryl C3,5),
133.87 (aryl C1), 135.26 (aryl C4), 167.77 (CCNNH). IR (KBr)
n(cm21): 1630 (nCNN). MS (EI): m/z 222.1 (M).
p-Morpholinobenzonitrile (19). A mixture of yttrium
trifluoromethanesulfonate (0.1 mmol, 0.08 g), p-chlorobenzoni-
trile (10 mmol, 1.37 g) and anhydrous morpholine (20 mmol,
1.8 ml) was heated under argon in a screw-cap sealed reaction
vessel in an aluminium block20 at 200 °C for 24 h. The crude
product was extracted with acetone (2 3 10 ml) and filtered.
The filtrate was purified by column chromatography on silica
gel using hexane–ethyl acetate 7+3 as the eluent. p-Morpholino-
benzonitrile (19) (1.12 g, 60%) was eluted first followed by
morpholino-p-chlorobenzamidine (21) (0.12 g, 6%).
Morpholinobenzonitrile (19). Mp 79.6–82.3 °C (hexane–
ethyl acetate). 1H NMR (300 MHz, CDCl3, TMS as internal
ref.) d 3.27 (t, J 5.0 Hz, 4H, H2A,6A), 3.85 (t, J 5.0 Hz, 4H, H3A,5A),
6.84–6.87 and 7.43–7.50 (4H, aryl). 13C NMR (300 MHz,
CDCl3, TMS as internal ref.) d 47.26 (C2A), 66.47 (C3A), 100.93
(C1), 114.04 (C3,5), 119.85 (CN), 133.53 (C2,6), 153.44 (C4). IR
(KBr) n(cm21): 2215 (nCNN), 1605, 1515 (nCNC). Analysis:
Calc. for C11H12N2O: C 70.19, H 6.43, N 14.88. Found: C
70.11, H 6.58, N 15.09%. MS (EI): m/z 188.1 (M).
Morpholino-p-chlorobenzamidine (21). Mp 69–70.7 °C
(hexane–ethyl acetate). 1H NMR (300 MHz, CDCl3, TMS as
internal ref.) d 3.2–3.9 (m, 9H, morpholine and NH), 7.33–7.43
(4H, aryl). 13C NMR (300 MHz, CDCl3, TMS as internal ref.)
d 66.82 (morpholine C3,5), 128.64 (phenyl C2,6), 128.85 (phenyl
C3,5), 133.57 (phenyl C1), 136.04 (phenyl C4), 169.34 (CNN). IR
(KBr) n(cm21): 1625 (nCNN): MS (EI): m/z 224.1 (M).
4-Hydroxybenzonitrile (17). A mixture of yttrium tri-
fluoromethanesulfonate (0.1 mmol, 0.08 g), p-methoxybenzoni-
342 Green Chemistry, 2002, 4, 339–343
trile (5) (10 mmol, 1.332 g) and anhydrous piperidine (10 mmol,
1ml) was heated under argon in a screw-cap sealed reaction
vessel in an aluminium block20 at 200 °C for 24 h. The crude
product was extracted with dichloromethane (30 ml) and
filtered. The filtrate was purified by flash chromatography on
silica gel using hexane–ethyl acetate, in a gradient 9+1 to 1+1,
as the eluent to give 4-hydroxybenzonitrile (17) (0.64 g, 54%).
1H NMR (300 MHz, CDCl , TMS as internal ref.) d 6.92–6.97
3
and 7.53–7.58 (4H, aryl). 13C NMR (300 MHz, CDCl3, TMS as
internal ref.) d 103.03 (C1), 116.42 (C3,5), 119.23 (CN), 134.28
(C2,6), 160.18 (C4). IR (KBr) n(cm21): 3290 (nOH), 2235
(nCNN).
Synthesis of 2,4,6-trisubstituted 1,3,5-triazines
Method A. Classical heating. A mixture of yttrium
trifluoromethanesulfonate (0.1 mmol, 0.08 g), the appropriate
nitrile (10 mmol) and anhydrous piperidine (10 mmol, 1 ml)
was heated under argon in a screw-cap sealed reaction vessel in
an aluminium block20 at 200 °C for 24 h. Purification was
performed as indicated in each case.
Method B. Synthesis using microwave irradiation. A
mixture of yttrium trifluoromethanesulfonate (0.1 mmol, 0.08
g), the appropriate nitrile (10 mmol) and anhydrous piperidine
(10 mmol, 1 ml) was introduced into a closed Pyrex flask and
irradiated in a modified PROLABO Maxidigest microwave
reactor21 at the power/time shown in Table 1.
Method C. Reactions with silica-supported Lewis acids. A
mixture of silica-supported Lewis acid [Si(Zn), Si(Al), Si(Ti)]
(0.2 mmol, 1 g), the appropriate nitrile (10 mmol) and
anhydrous piperidine (10 mmol, 1 ml) was heated under the
conditions described in methods A or B as appropriate. The
crude product was extracted with the appropriate solvent and
silica gel was removed by filtration.
2,4,6-Tris(4-trifluoromethylphenyl)-1,3,5-triazine (12).
Method A. From p-trifluoromethylbenzonitrile (4) (10
mmol, 1.71 g) for 12 h. The crude product was triturated with
diethyl ether (3 3 15 ml) and filtered off to give the product as
a white solid (0.71 g, 42%). mp 276.5–278.5 °C (toluene). 1H
NMR (300 MHz, CDCl3, TMS as internal ref.) d 7.85 (d, J 8.8
Hz, 6H, H2,6), 8.88 (d, J 8.8 Hz, 6H, H3,5). 13C NMR (300 MHz,
CDCl3, TMS as internal ref.) d 125.72 (C3,5), 129.35 (C2,6),
134.4 (q, J 32.73 Hz, C4), 138.75 (C1), 171.04 (Ctriazine). IR
(KBr) n(cm21): 1528 (nCNC, nCNN) 1321 (nC–F). Analysis: Calc.
for C24H12F9N3: C 56.15, H 2.36, N 8.18. Found: C 56.64, H
2.52, N 8.32%. MS (EI): m/z 513 (M).
2,4,6-Trispiperidino-1,3,5-triazine (10).
Method A. From 1-cyanopiperidine (2) (10 mmol, 1.10 g) for
12 h. The crude product was triturated with diethyl ether (3 3
15 ml) and filtered off to give the product as a white solid (0.34
g, 31%). mp 206–209.5 °C. 1H NMR (300 MHz, CDCl3, TMS
as internal ref.) d 1.48–1.68 (m, 18H, H3A,5A,4A), 3.70 (t, J 5.4 Hz,
12H, H2A,6A). 13C NMR (300 MHz, CDCl3, TMS as internal ref.)
d 25.34 (C4A), 26.07 (C3A,5A), 44.30 (C2A,6A), 165.67 (Ctriazine). IR
(KBr) n(cm21): 1532, 1480 n(CNC, nCNN). MS (EI): m/z 330.2
(M).
2,4,6-Trismorpholino-1,3,5-triazine (9).
Method A. From morpholinocarbonitrile (1) (10 mmol, 1.12
g) and morpholine (10 mmol, 0.9 ml). The crude product was
triturated with diethyl ether (3 3 15 ml) and filtered off to give
the product as a white solid (0.94 g, 84%). mp 272–275 °C
(toluene). 1H NMR (300 MHz, CDCl3, TMS as internal ref.) d
3.68 (m, 24H, morpholine). 13C NMR (300 MHz, CDCl3, TMS
as internal ref.) d 43.61 (C2,6), 66.87 (C3,5), 165.32 (Ctriazine). IR
(KBr) n(cm21): 1548, 1480, 1453 n(CNN, nCNC). Analysis: Calc.
C15H24N6O3: C 53.56, H 7.19, N 24.98. Found: C 53.80, H 7.22,
N 28.37%. MS (EI): m/z 336.2 (M).
2,4,6-Tris(4-morpholinophenyl)-1,3,5-triazine (14).
Method A. From p-morpholinobenzonitrile (19) (5.18 mmol,
0.975 g) and morpholine (9 mmol, 0.8 ml) for 72 h. The crude
product was extracted with dichloromethane (2 3 10 ml) and
filtered. The filtrate was purified by column chromatography
firstly using hexane–ethyl acetate (7+3), then ethyl acetate and
finally ethyl acetate–diethylamine (2%). 2,4,6-(4-Morpholino-
phenyl)-1,3,5-triazine (14) (0.172 g, 18%) eluted first, followed
by morpholino-p-morpholinobenzamidine (22) (0.110 g,
12%).
2,4,6-Tris(morpholinophenyl)-1,3,5-triazine (14). Mp
269.7–271.6 °C (decomp.). 1H NMR (300 MHz, CDCl3, TMS
as internal ref.) d 3.33–3.36 and 3.89–3.93 (24 H, morpholine),
7.01–7.04 and 8.64–8.67 (12H, aryl). 13C NMR (300 MHz,
CDCl3, TMS as internal ref.) d 48.04 (C2A,6A), 66.69 (C3A,5A),
114.06 (C3,5), 130.23 (C2,6), 170.44 (Ctriazine). IR (KBr)
n(cm21): 1608, 1495 n(CNC, nCNN). Analysis: Calc.
C33H36N6O3: C 70.19, H 6.09, N 14.88. Found: C 69.70, H 6.09,
N 14.41%. MS (EI): m/z 564.4 (M).
Morpholino-p-morpholinobenzamidine (22). Mp
120.6–123.2 °C. 1H NMR (300 MHz, CDCl3, TMS as internal
ref.) d 3.19 (t, J 4.9 Hz, 4H, H2A,6A morpholino-phenyl), 3.5–3.75
(m, 8H, morpholine), 3.84 (t, J 4.9 Hz, 4H, H3A,5A morpholino-
phenyl), 6.8–6.9 and 7.3–7.4 (4H, aryl). 13C NMR (300 MHz,
CDCl3, TMS as internal ref.) d 48.28 (morpholine C2,6),
66.47–66.85 (morpholine C3,5), 114.30 (aryl C3,5), 125.47 (aryl
C1), 128.54 (aryl C2,6), 152.24 (aryl C4), 170.49 (CNN). IR
(KBr) n(cm21): 3220 n(NH), 1625 n(CNN). MS (EI): m/z 276.3
(M + 1).
Acknowledgments
Financial support from the Spanish DGI (project BQU2001-
1095) is gratefully acknowledged.
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