Condensation of aromatic aldehydes with 5,5-dimethyl-1,3-cyclohexanedione without catalyst

Article abstract of DOI:10.1081/SCC-120012999

The condensation of aromatic aldehyde with 5,5-dimethyl-1,3-cyclohexanedione is carried out in ethylene glycol as solvent without catalyst.

Full text of DOI:10.1081/SCC-120012999

This article was downloaded by: [Aston University]
On: 26 January 2014, At: 00:38
Publisher: Taylor & Francis
Informa Ltd Registered in England and Wales Registered Number: 1072954 Registered office: Mortimer House,
37-41 Mortimer Street, London W1T 3JH, UK
Synthetic Communications: An International Journal
for Rapid Communication of Synthetic Organic
Chemistry
Publication details, including instructions for authors and subscription information:
http://www.tandfonline.com/loi/lsyc20
CONDENSATION OF AROMATIC ALDEHYDES WITH
5,5-DIMETHYL- 1,3-CYCLOHEXANEDIONE WITHOUT
CATALYST
a
b
a
a
a
a
Shujiang Tu , Jianfeng Zhou , Zaisheng Lu , Xu Deng , Daqing Shi & Suhui Wang
a
Department of Chemistry , Xuzhou Normal University , Xuzhou, 221009, P.R. China
b
Department of Chemistry , Huaiyin Normal College , Huaiyin, P.R. China
Published online: 16 Aug 2006.
To cite this article: Shujiang Tu , Jianfeng Zhou , Zaisheng Lu , Xu Deng , Daqing Shi & Suhui Wang (2002) CONDENSATION
OF AROMATIC ALDEHYDES WITH 5,5-DIMETHYL- 1,3-CYCLOHEXANEDIONE WITHOUT CATALYST, Synthetic Communications:
An International Journal for Rapid Communication of Synthetic Organic Chemistry, 32:19, 3063-3067, DOI: 10.1081/
SCC-120012999
To link to this article: http://dx.doi.org/10.1081/SCC-120012999
PLEASE SCROLL DOWN FOR ARTICLE
Taylor & Francis makes every effort to ensure the accuracy of all the information (the “Content”) contained
in the publications on our platform. However, Taylor & Francis, our agents, and our licensors make no
representations or warranties whatsoever as to the accuracy, completeness, or suitability for any purpose of the
Content. Any opinions and views expressed in this publication are the opinions and views of the authors, and
are not the views of or endorsed by Taylor & Francis. The accuracy of the Content should not be relied upon and
should be independently verified with primary sources of information. Taylor and Francis shall not be liable for
any losses, actions, claims, proceedings, demands, costs, expenses, damages, and other liabilities whatsoever
or howsoever caused arising directly or indirectly in connection with, in relation to or arising out of the use of
the Content.
This article may be used for research, teaching, and private study purposes. Any substantial or systematic
reproduction, redistribution, reselling, loan, sub-licensing, systematic supply, or distribution in any
form to anyone is expressly forbidden. Terms & Conditions of access and use can be found at http://
www.tandfonline.com/page/terms-and-conditions

MARCEL DEKKER, INC. • 270 MADISON AVENUE • NEW YORK, NY 10016
©
2002 Marcel Dekker, Inc. All rights reserved. This material may not be used or reproduced in any form without the express written permission of Marcel Dekker, Inc.
SYNTHETIC COMMUNICATIONS
Vol. 32, No. 19, pp. 3063–3067, 2002
CONDENSATION OF AROMATIC
ALDEHYDES WITH 5,5-DIMETHYL-
1
,3-CYCLOHEXANEDIONE
WITHOUT CATALYST
1
,
2
1
Shujiang Tu, * Jianfeng Zhou, Zaisheng Lu,
1
Xu Deng, Daqing Shi, and Suhui Wang
1
1
1
Department of Chemistry, Xuzhou Normal University,
Xuzhou 221009, P.R. China
Department of Chemistry, Huaiyin Normal College,
Huaiyin, P.R. China
2
ABSTRACT
The condensation of aromatic aldehyde with 5,5-dimethyl-
,3-cyclohexanedione is carried out in ethylene glycol as
solvent without catalyst.
1
Key Words: Aromatic aldehydes; 5,5-Dimethyl-1,3-cyclo-
hexanedione; Condensation reaction
Condensation reaction of carbonyl compounds with active methylene
compounds is one of the most important synthetic methods of substituted
[
1]
alkenes. The reactions are generally catalyzed by bases or Lewis acids.
Recently, inorganic solid supports as catalysts, resulting in higher selectivity,
milder conditions and easier work-up, has been reported as useful catalysts
[
for Knoevenagel reaction. Thus, aluminium oxide, xonotlite, AlPO4–
2]
[3]
[
4]
[5]
[6]
[7]
Al O , KF–Al O , K10–ZnCl2 and cadmium iodide have been
2
3
2
3
*
Corresponding author. E-mail: laotu2001@263.net
3
063
DOI: 10.1081/SCC-120012999
Copyright & 2002 by Marcel Dekker, Inc.
0039-7911 (Print); 1532-2432 (Online)
www.dekker.com

MARCEL DEKKER, INC. • 270 MADISON AVENUE • NEW YORK, NY 10016
©
2002 Marcel Dekker, Inc. All rights reserved. This material may not be used or reproduced in any form without the express written permission of Marcel Dekker, Inc.
3
064
TU ET AL.
[
8]
0
reported. In our previous paper, we reported that 2,2 -arylmethylene-
bis(3-hydroxyl-5,5-dimethyl-2-cyclohexen-1-one) was obtained by reaction
of aromatic aldehyde with 5,5-dimethyl-1,3-cyclohexanedione in DMF as
solvent without catalyst. However, treatment of aromatic aldehyde with
5,5-dimethyl-1,3-cyclohexanedione in ethylene glycol as solvent without
catalyst, Knoevenagel condensation, Michael addition, cyclodehydration
have taken place and 3,3,6,6-tetramethyl-9-aryl-1,8-dioxo-2,3,4,5,6,7-hexa-
hydroanthene are obtained in excellent yield. In this paper, we would like to
report that the condensation of aromatic aldehyde with 5,5-dimethyl-
1,3-cyclohexanedione is carried out in ethylene glycol as solvent without
catalyst. We also present the crystal structure of 3e.
The results were listed in Table 1.
All the compounds obtained gave analysis for C, H, N in good agree-
ment to calculated values. The structures were established on the basis of
spectroscopic data and confirmed by X-ray diffraction studies on
[9]
monocrystal of 3e (Fig. 1).
EXPERIMENTAL
Melting points were determined in open capillaries and are uncor-
1
rected. IR spectra were recorded on a FT IR-8101 spectrometer. HNMR
spectra were measured on a JEOL FX-90Q spectrometer using TMS as
internal standard. Elemental analysis were determined using Perkin-Elmer
240C elemental analyser. X-ray diffraction were measured on a Rigaku 7R
CAD4 diffractometer.
General Procedure
A dry 50 mL flask was charged with aromatic aldehyde (5 mmol),
,5-dimethyl-1,3-cyclohexanedione (10 mmol) and ethylene glycol (15 mL).
5
The mixture was kept at 80 C for 1.5 h, then cooled to room temperature.
ꢀ

MARCEL DEKKER, INC. • 270 MADISON AVENUE • NEW YORK, NY 10016
©
2002 Marcel Dekker, Inc. All rights reserved. This material may not be used or reproduced in any form without the express written permission of Marcel Dekker, Inc.
CONDENSATION OF AROMATIC ALDEHYDES
3065
Table 1. Condensation of Aromatic Aldehydes 1a–j with 2
ꢀ
Entry
Ar
Yield (%)
M.P. ( C)
3
3
3
3
3
3
3
3
3
3
a
b
c
d
e
f
g
h
i
C
6
H
5
94
92
90
99
96
95
97
98
96
93
198–200
218–220
246–248
222–224
230–231
228–229
246–248
216–218
224–226
170–172
4-CH C H
4
3
6
2-NO
4-NO
2
2
C
6
H
4
C
6
H
4
4-ClC H
6
4
2-ClC
4-HOC
6
H
4
6
H
4
3,4-OCH OC H
2
6
3
4-CH
3,4-(CH
3
OC
6 4
H
j
3
O)
2
-C
6
H
3
Figure 1. X-ray crystal structure of 3e.
The reaction mixture was poured into 150 mL water. The solid was filtered
off, then washed with water. The crude solid was purified by recrystalliza-
tion from 95% EtOHto give 3a–j.
ꢀ
[10]
ꢀ
À1
1
3
a: M.p. 198–200 C (Lit.
680, 1665, 1625, 1470, 1360, 1200, 1170, 1140, 1000, 745, 700; HNMR
CDCl , ꢁ, ppm): 0.98 (6H, s, 2 Â CH ), 1.10 (6H, s, 2 Â CH ), 2.06–2.18
204–205 C); IR (KBr, ꢀ, cm ): 2980,
1
(
3
3
3

MARCEL DEKKER, INC. • 270 MADISON AVENUE • NEW YORK, NY 10016
©
2002 Marcel Dekker, Inc. All rights reserved. This material may not be used or reproduced in any form without the express written permission of Marcel Dekker, Inc.
3
066
TU ET AL.
(
Found (%): C, 79.01; H, 7.33; Calcd. for C H O : C, 78.83; H, 7.47.
8H, m, 4 Â CH ), 4.66 (1H, s, CH), 7.21 (5H, s, ArH); Elemental analysis:
2
2
3
26
3
ꢀ
À1
1
3
b: M.p. 218–220 C; IR (KBr, ꢀ, cm ): 2980, 1680, 1665, 1630, 1510,
470, 1360, 1200, 1170, 1140, 790, 770; HNMR (CDCl , ꢁ, ppm): 0.98
1
3
(
(
6H, s, 2 Â CH ), 1.10 (6H, s, 2 Â CH ), 2.07–2.20 (8H, m, 4 Â CH ), 2.42
3
3
3
2
3H, s, CH –Ar), 4.69 (1H, s, CH), 6.80–7.28 (4H, m, ArH); Elemental analy-
sis: Found (%): C, 79.28; H, 7.53; Calcd. for C H O : C, 79.08; H, 7.74.
2
4
28
3
ꢀ
À1
3
c: M.p. 246–248 C; IR (KBr, ꢀ, cm ): 2980, 1680, 1670, 1620, 1530,
360, 1210, 1170, 1150, 1010, 860, 800, 780, 740, 700; HNMR (CDCl , ꢁ,
1
1
3
ppm): 0.98 (6H, s, 2 Â CH ), 1.10 (6H, s, 2 Â CH ), 2.03–2.18 (8H, m,
3
3
4
Found (%): C, 69.96; H, 6.43; N, 3.31; Calcd. for C H NO : C, 69.85; H,
 CH ), 5.61 (1H, s, CH), 7.36–7.44 (4H, m, ArH); Elemental analysis:
23 25 5
2
6
.37; N, 3.54.
d: M.p. 222–224 C; (Lit.
650, 1620, 1520, 1360, 1340, 1200, 1070, 1040, 1000, 870, 830; HNMR
ꢀ
[10]
ꢀ
À1
3
222 C) IR (KBr, ꢀ, cm ): 2980, 1660,
1
1
(
(
CDCl , ꢁ, ppm): 0.99 (6H, s, 2 Â CH ), 1.12 (6H, s, 2 Â CH ), 2.06–2.21
2
3
3
3
8H, m, 4 Â CH ), 4.76 (1H, s, CH), 7.50–7.63 (2H, m, ArH), 8.06–8.18 (2H,
m, ArH); Elemental analysis: Found (%): C, 69.91; H, 6.60; N, 3.29; Calcd.
for C H NO : C, 69.85; H, 6.37; N, 3.54.
2
3
25
5
ꢀ
À1
3
e: M.p. 230–231 C; IR (KBr, ꢀ, cm ): 2980, 1680, 1660, 1620, 1490,
1
480, 1360, 1200, 1170, 1140, 1090, 1010, 1000, 850, 840; HNMR (CDCl ,
1
3
ꢁ
, ppm): 0.98 (6H, s, 2 Â CH ), 1.10 (6H, s, 2 Â CH ), 2.03–2.14 (8H,
3
3
m, 4 Â CH ), 4.64 (1H, s, CH), 7.26 (4H, s, ArH); Elemental analysis:
2
Found (%): C, 71.92; H, 6.32; Calcd. for C H ClO : C, 71.77; H, 6.54.
3
2
3
25
ꢀ
[10]
ꢀ
À1
3
f: M.p. 228–229 C (Lit. 224–226 C); IR (KBr, ꢀ, cm ): 2980, 1680,
1
660, 1620, 1490, 1470, 1360, 1200, 1170, 1140, 1100, 1000, 850, 840;
1
HNMR (CDCl , ꢁ, ppm): 0.98 (6H, s, 2 Â CH ), 1.10 (6H, s, 2 Â CH ),
3
3
3
2
.06–2.19 (8H, m, 4 Â CH ), 4.64 (1H, s, CH), 7.26 (4H, s, ArH); Elemental
2
analysis: Found (%): C, 71.98; H, 6.39; Calcd. for C H ClO : C, 71.77; H,
23 25 3
6
.54.
ꢀ
[10]
ꢀ
À1
3
g: M.p. 246–248 C (Lit.
246 C); IR (KBr, ꢀ, cm ): 3360, 2980,
790, 1720, 1700, 1630, 1610, 1520, 1390, 1370, 1260, 1230, 1200, 1190, 850,
1
8
2
6
1
40; HNMR (CDCl , ꢁ, ppm): 0.99 (6H, s, 2 Â CH ), 1.10 (6H, s, 2 Â CH ),
3
3
3
.03–2.31 (8H, m, 4 Â CH ), 4.62 (1H, s, CH), 6.77 (2H, d, J ¼ 8 Hz, ArH),
2
.98 (2H, d, J ¼ 8 Hz, ArH); Elemental analysis: Found (%): C, 75.24;
H, 7.06; Calcd. for C H O : C, 75.38; H, 7.15.
2
3
26
4
ꢀ
À1
3
h: M.p. 216–218 C; IR (KBr, ꢀ, cm ): 2980, 1720, 1630, 1565, 1510,
1
490, 1440, 1380, 1360, 1320, 1270, 1230, 1040, 940, 920, 890, 810, 790;
1
HNMR (CDCl , ꢁ, ppm): 1.00 (6H, s, 2 Â CH ), 1.10 (6H, s, 2 Â CH ),
3
3
3
2
6
6
.06–2.30 (8H, m, 4 Â CH ), 4.58 (1H, s, CH), 5.90 (2H, s, OCH O),
2
2
.69–6.78 (3H, m, ArH); Elemental analysis: Found (%): C, 73.18; H,
.76; Calcd. for C H O : C, 73.07; H, 6.64.
2
4
26
5

MARCEL DEKKER, INC. • 270 MADISON AVENUE • NEW YORK, NY 10016
©
2002 Marcel Dekker, Inc. All rights reserved. This material may not be used or reproduced in any form without the express written permission of Marcel Dekker, Inc.
CONDENSATION OF AROMATIC ALDEHYDES
3067
ꢀ
À1
3
i: M.p. 224–226 C; IR (KBr, ꢀ, cm ): 2980, 1680, 1660, 1620, 1510,
1
450, 1370, 1360, 1260, 1230, 1190, 1170, 1140, 1030, 1000, 840; HNMR
1
(
CDCl , ꢁ, ppm): 1.01 (6H, s, 2 Â CH ), 1.09 (6H, s, 2 Â CH ), 2.20 (4H, s,
3
3
3
2
6
7
 CH ), 2.46 (4H, s, 2  CH ), 3.73 (3H, s, CH O), 4.70 (1H, s, CH),
2
2
3
.67–7.28 (4H, m, ArH); Elemental analysis: Found (%): C, 75.84; H,
.22; Calcd. for C H O : C, 75.76; H, 7.41.
2
4
28
4
ꢀ
À1
3
j: M.p. 170–172 C; IR (KBr, ꢀ, cm ): 2980, 1580, 1520, 1470, 1420,
380, 1360, 1255, 1240, 1150, 1030, 890, 870, 800, 760; HNMR (CDCl , ꢁ,
1
1
3
ppm): 0.99 (6H, s, 2 Â CH ), 1.10 (6H, s, 2 Â CH ), 2.19 (4H, s, 2 Â CH ),
3
3
2
2
.45 (4H, s, 2 Â CH ), 3.80 (6H, s, 2 Â CH O), 4.70 (1H, s, CH), 6.76–6.90
2
3
(3H, m, ArH); Elemental analysis: Found (%): C, 73.30; H, 7.45; Calcd. for
C H O : C, 73.14; H, 7.36.
2
5
30
5
REFERENCES
1. Jone, G. Organic Reactions. Wiley: New York, 1967; Vol. 15, p. 204.
2. Texier-Boullet, F.; Foucaud, A. Tetrahedron Lett. 1982, 23, 4927.
3. Chalais, S.; Laszlo, P.; Mathy, A. Tetrahedron Lett. 1985, 26, 4453.
4. Cabello, J.A.; Campelo, J.M.; Garcia, A.; Luna, D.; Marinas, J.M. J.
Org. Chem. 1984, 49, 5195.
5. Gao, Y.; Shi, D.Q.; Zhou, L.H.; Dai, G.Y. Youji Huaxue(CH) 1996,
16(6), 548; Chem. Abstr. 126(1997)171372x.
6. Villemin, D.; Martin, B.J. Chem. Res. (S) 1994, (4), 146.
7. Prajapati, D.; Sanduh, J.S. J. Chem. Soc., Perkin Trans. I 1993, 739.
8. Shi, D.Q.; Wang, Y.C.; Lu, Z.S.; Dai, G.Y. Synth. Commun. 2000,
30(4), 713.
9
. X-ray analysis of 3e: Empirical formula C H ClO , F.W. 384.90,
2
3
25
3
˚
T ¼ 293 K, monoclinic, space group P2 /n, a ¼ 6.048(1) A, b ¼
1
3
˚
˚
˚
˚
1
9.543(4) A, c ¼ 17.420(3) A, ꢂ ¼ 97.29(1) A, V ¼ 2042.2(6) A , Z ¼ 4,
À3
À1
˚
D ¼ 1.252 g cm , F(000) ¼ 816, l(MoKa) ¼ 0.71069 A, ꢃ ¼ 2.06 cm
,
c
ꢀ
À3
˚
6
<2ꢄ<51 , R ¼ 0.039, R ¼ 0.047, largest diff. peak 0.18 eA
.
w
1
0. Horning, E.C.; Horning, M.G. J. Org. Chem. 1946, 11, 95.
Received in Japan April 4, 2001

MARCEL DEKKER, INC. • 270 MADISON AVENUE • NEW YORK, NY 10016
©
2002 Marcel Dekker, Inc. All rights reserved. This material may not be used or reproduced in any form without the express written permission of Marcel Dekker, Inc.