Microwave assisted synthesis of 2,4,6-triarylamino-1,3,5-triazines as potential UV absorbent

Article abstract of DOI:10.1081/SCC-120021979

2,4,6-Triarylamino-1,3,5-triazines was synthesized in a few minutes by reaction of cyanuric chloride with aromatic amines under microwave irradiation. This method is featured with rapid reaction, convenient operation, high yield, and clean. UV-absorption was tested for each compound.

Full text of DOI:10.1081/SCC-120021979

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Microwave Assisted Synthesis of 2,4,6-
Triarylamino-1,3,5-triazines as Potential UV Absorbent
Yaowu Sha a & Yuyi Dong a
a Department of Chemistry, Tsinghua University, Beijing, P.R. China
Published online: 17 Aug 2006.
To cite this article: Yaowu Sha & Yuyi Dong (2003): Microwave Assisted Synthesis of 2,4,6-Triarylamino-1,3,5-triazines as
Potential UV Absorbent, Synthetic Communications: An International Journal for Rapid Communication of Synthetic Organic
Chemistry, 33:15, 2599-2604
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SYNTHETIC COMMUNICATIONSÕ
Vol. 33, No. 15, pp. 2599–2604, 2003
Microwave Assisted Synthesis of
2,4,6-Triarylamino-1,3,5-triazines
as Potential UV Absorbent
*
Yaowu Sha and Yuyi Dong
Department of Chemistry, Tsinghua University,
Beijing, P.R. China
ABSTRACT
2,4,6-Triarylamino-1,3,5-triazines was synthesized in a few minutes
by reaction of cyanuric chloride with aromatic amines under
microwave irradiation. This method is featured with rapid reaction,
convenient operation, high yield, and clean. UV-absorption was
tested foreach compound.
Key Words: Microwave; 2,4,6-Triarylamino-1,3,5-triazine; UV-
absorbent.
*Correspondence: Yaowu Sha, Department of Chemistry, Tsinghua University,
Beijing, 100084, P.R. China; E-mail: shayw@mail.tsinghua.edu.cn.
2599
DOI: 10.1081/SCC-120021979
Copyright & 2003 by Marcel Dekker, Inc.
0039-7911 (Print); 1532-2432 (Online)
www.dekker.com

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2600
Sha and Dong
1. INTRODUCTION
Since Gedyes et al.’s[1] application of microwave irradiation in
organic synthesis, microwave irradiation (MWI) has been introduced
into each aspect of organic chemistry.[2,3] In recent years there has
been increasing interest on 1,3,5-triazine chemistry, because of its molec-
[4–8]
ularsymmetyr
and electronic properties.[9,10] Microwave assisted
synthesis of 2,4,6-triaryloxy-1,3,5-triazines has been reported.[11] 2,4,6-
Triarylamino-1,3,5-triazines have practical application in reactive
dye,[12] printing ink components,[13,14] UV-filters in light screening
compositions,[15] and chiral solvating agent.[16] This kind of compounds
was all synthesized from cyanuric chloride and corresponding aliphatic
or aromatic amines in a few days, although sodium or sodium hydride
were used to promote the reaction and at as high as 300ꢀC
in some articles. So, it is important to find a simple and fast synthetic
method.
2. RESULTS AND DISCUSSION
The microwave assisted synthesis of 2,4,6-triarylamino-1,3,5-tri-
azines(III) was through the reaction of cyanuric chloride(I) with aromatic
amines(II) (Sch. 1) in a mixed solvent (1,4-dioxane:DMF). Sodium
hydrogen carbonate was used as base.
Results are shown on Table 1. Through microwave irradiation, the
reaction time was shortened to a few minutes from a few days reported.
HPLC analysis of the reaction mixture showed little side product.
Products have good absorption between 250 nm to 400 nm, they are
potential UV-absorbent.
The microwave assisted synthesis of 2,4,6,-triarylamino-1,3,5-tri-
azines has the feature of rapid reaction, convenient operation, high yield,
and clean.
NHAr
N
Cl
NaHCO3
Dioxane-DMF
N
N
N
+ 3ArNH2
Cl
MWI
ArHN
N
NHAr
Cl
N
(I)
(II)
(III)
Scheme 1. Reaction of cyanuric chloride with aromatic amines.

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2,4,6-Triarylamino-1,3,5-triazines
Table 1. Synthesis of 2,4,6-triarylamino-1,3,5-triazines.b
2601
Reaction time Yield
(%)
M.p.
(ꢀC)
UV-ꢀmax
(nm)
Entry III
Ar
(min)
III-1
III-2
Phenyl
2
2
2
2
2.5
2
2
2
2
3
2
3
2
2
2
3
96
95
95
98
86
90
94
97
95
82
95
85
98
94
95
80
239 (232)[18] 270, 280
2-Me-phenyl
3-Me-phenyl
4-Me-phenyl
2,6-Di-Me-phenyl
2-F-phenyl
233–234
232–233
238–239
259–261
173–174
244–245
184–186
202–204
182–183
172–173
145–148
262–264
274–276
136–138
154–160
265
265
III-3
III-4
270, 285
240
263
III-5
III-6
III-7
III-8
3-F-phenyl
4-F-phenyl
268
268, 290
260
III-9
2,4-F2-phenyl
2,5-F2-phenyl
2-Cl-phenyl
III-10
III-11
III-12
III-13
III-14
III-15
III-16
263, 290
270
270
3-Cl-phenyl
4-Cl-phenyl
270, 290
282
4-Br-phenyl
2,4,6-Br3-phenyl
4-NO2-phenyl
248, 315
360
bIII-2–16 are new compounds.[19]
3. EXPERIMENTAL
3.1. General Consideration
The microwave oven is S^MSUNG-S7A73, 650 W, 2450 Hz. Middle
fire was used. Through a hole on the top of oven, the reaction flask was
linked to a outside refluxing column.[17]
3.2. General Procedure
To a 50 mL round bottom flask was added 1.8 g (0.01 mol) cyanuric
chloride, 15 mL 1,4-dioxane, 4.5 mL DMF, 2.5 g sodium hydrogen
carbonate, and 0.03 mol aromatic amine. The flask was then put into
microwave oven and connected with refluxing column. After microwave
irradiation, solvent was distilled out under reduced pressure and a solid
was obtained. This solid was washed thoroughly with water, dried, and
then recrystallized from suitable solvent. All compounds have passed the
elemental analysis, FAB-MS, IR, and UV-absorption.

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2602
Sha and Dong
REFERENCES
1. Gedye, R.; Smith, F.; Westaway, K.; Ali, H.; Baldisera, L.;
Laberge, L.; Rousell, J. The use of microwave-ovens for rapid
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2. Loupy, A. Solvent-free reactions. Topics in Current Chemistry
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3. Sha, Y.W.; Wang, Y.; Ge, J.; Wang, X. Application of microwave
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4. Thallapally, P.K.; Chakraborty, K.; Carrell, H.L.; Kotha, S.;
Desiraju, G.R. Shape and size effects in the crystal structures of
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9. Munakata, M.; Wen, M.; Suenaga, Y.; Kuroda-Sowa, T.;
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10. Boraei, A.A.A.; El-Roudi, O.M. Charge transfer molecular
complexes of some azines with iodine. Can. J. Appl. Spec. 1996,
41 (2), 37–41.

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2,4,6-Triarylamino-1,3,5-triazines
2603
11. Sagar, A.D.; Patil, D.S.; Bandgar, B.P. Microwave assisted
synthesis of triaryl cyanurates. Synthetic Commun. 2000, 30 (10),
1719–1723.
12. Kunimi, N.; Sasaki, S.; Toishi, K.; Inoue, A. Monoazo Compound
and an Intermediate for a Fiber-Reactive Dye Compound. US
Patent 5,962,655, October5, 1999.
13. Georges, M.; Dieter, R.; Helmut, L. Triazinderivate als UV-Filter in
Sonnenschutzmitteln. EP 0,818,450, August 7, 1996.
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0,933,376, August 4, 1999.
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19. III-1. FAB-MS m/z: 355.28 (M þ H)þ (100%), 377.15 (M þ Na)þ
(15%); III-2. FAB-MS m/z: 397.85 (M þ H)þ (100%), 419.38
(M þ Na)þ, (50%); Anal. calcd. forC 24H24N6: C 72.70, H 6.10, N
21.20. Found: C 72.55, H 6.15, N 21.20; III-3. FAB-MS m/z: 397.35
(M þ H)þ (100%), 419.19 (M þ Na)þ (10%). Anal. calcd. for
C24H24N6: C 72.70, H 6.10, N 21.20. Found: C 72.46, H 5.95, N
21.19; III-4. FAB-MS m/z: 397.37 (M þ H)þ (100%), 419.17
(M þ Na)þ (20%). Anal. calcd. forC 24H24N6: C 72.35, H 6.10, N
21.20. Found: C 72.60, H 6.08, N 21.16; III-5. FAB-MS m/z: 439.90
(M þ H)þ (100%), 461.63 (M þ Na)þ (10%). Anal. calcd. for
C27H30N6: C 73.94, H 6.89, N 19.16. Found: C 73.87, H 6.85, N
19.15; III-6. FAB-MS m/z: 409.23 (M þ H)þ (100%), 431.14
(M þ Na)þ (75%). Anal. calcd. forC 21H15F3N6: C 61.76, H 3.70,
N 20.58. Found: C 61.73, H 3.72, N 20.55; III-7. FAB-MS m/z:
409.19 (M þ H)þ (100%), 431.13 (M þ Na)þ (15%). Anal. calcd.
forC 21H15F3N6: C 61.76, H 3.70, N 20.58. Found: C 61.74, H
3.71, N 20.59; III-8. FAB-MS m/z: 409.18 (M þ H)þ (100%), 431.12
(M þ Na)þ (45%). Anal. calcd. forC 21H15F3N6: C 61.76, H 3.70, N
20.58. Found: C 61.76, H 3.69, N 20.62; III-9. FAB-MS m/z: 463.12

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Sha and Dong
(M þ H)þ (100%), 485.05 (M þ Na)þ (25%). Anal. calcd. for
C21H12F6N6: C 54.55, H 2.62, N 18.18. Found: C 54.52, H 2.61,
N 18.22; III-10. FAB-MS m/z: 463.11 (M þ H)þ (100%), 485.05
(M þ Na)þ (30%). Anal. calcd. forC 21H12F6N6: C 54.55, H 2.62,
N 18.18. Found: C 54.51, H 2.63, N 18.21; III-11. FAB-MS m/z:
457.22 (M þ H)þ (100%), 459.12 (M þ H)þ (95%). Anal. calcd. for
C21H15Cl3N6: C 55.10, H 3.30, N 18.36. Found: C 55.13, H 2.29, N
18.33; III-12. FAB-MS m/z: 457.22 (M þ H)þ (90%), 459.12
(M þ H)þ (100%). Anal. calcd. forC 21H15Cl3N6: C 55.10, H 3.30,
N 18.36. Found: C 55.11, H 2.31, N 18.37; III-13. FAB-MS m/z:
457.23 (M þ H)þ (80%), 459.07 (M þ H)þ (100%). Anal. calcd. for
C21H15Cl3N6: C 55.10, H 3.30, N 18.36. Found: C 55.09, H 2.32, N
18.34; III-14. FAB-MS m/z: 437.2 (M-BrC6H3)þ (25%), 274.35 (M-
2BrC6H5)þ (80%). Anal. calcd. forC 21H15Br3N6: C 42.67, H 2.56,
N 14.22. Found: C 42.70, H 2.55, N 14.25; III-15. FAB-MS m/z:
767.32 (M þ Na-Br3C6H2)þ (5%), 454.11 (M þ Na-2Br3C6H3)þ
(5%). Anal. calcd. forC 21H9Br9N6: C 23.69, H 0.85, N 7.90.
Found:
C 23.64, H 0.84, N 7.92; III-16. FAB-MS m/z:
383.03 (M þ 2Na-NO2C6H4NH-O)þ (30%), 357.01 (M þ Na-H2O-
NO2C6H4NH-)þ (30%). Anal. calcd. forC 21H15N9O6: C 51.54, H
3.09, N 25.76. Found: C 51.56, H 3.10, 25.78.
Received in Japan September21, 2002