Reaction of a zwitterionic pyridinium ylide with N,N-dimethylaniline

Article abstract of DOI:10.1515/znb-2010-0118

1,3-Dimethyl-2,4,6-trioxo-5-pyridinomethyl-1,3-perhydrodiazin- 5-ylpyridinium ylide (3) reacts with N,N-dimethylaniline to give 5-((1,3-dimethyl-2,4,6-trioxo-hexahydropyrimidin-5-yl)methyl) -5-(4-(dimethylamino)benzyl)-1,3-dimethylpyrimidine- 2,4,6(1H3H5H)-trione (6) in good yield. The crystal structure of 6 is reported.

Full text of DOI:10.1515/znb-2010-0118

Note
99
(a)
(b)
Reaction of a Zwitterionic Pyridinium
Ylide with N,N-Dimethylaniline
Kamal Sweidana, Norbert Kuhnb,
Ca¨cilia Maichle-Mo¨ßmerb, and Manfred Steimannb
a Faculty of Pharmacy, Al-Zaytoonah University of Jordan,
P. O. Box 130, Amman, Jordan
b
Institut fu¨r Anorganische Chemie der Universita¨t
Tu¨bingen, Auf der Morgenstelle 18, 72076 Tu¨bingen,
Germany
Reprint requests to Dr. K. Sweidan.
E-mail: kamal sweidan@hotmail.com, or
Prof. Dr. N. Kuhn. E-mail: norbert.kuhn@uni-tuebingen.de
Z. Naturforsch. 2010, 65b, 99 – 100;
received August 13, 2009
1,3-Dimethyl-2,4,6-trioxo-5-pyridinomethyl-1,3-perhydro-
diazin-5-ylpyridinium ylide (3) reacts with N,N-dimethyl-
aniline to give 5-((1,3-dimethyl-2,4,6-trioxo-hexahydropyr-
imidin-5-yl)methyl)-5-(4-(dimethylamino)benzyl)-1,3-dime-
thylpyrimidine-2,4,6(1H3H5H)-trione (6) in good yield. The
crystal structure of 6 is reported.
(c)
Key words: Heterocycles, Barbituric Acid,
Crystal Structure
There has been much interest in barbituric acid
derivatives (1) in the past years owing to their poten-
tial application as drugs [1, 2]. Catalytic hydrogenation
of 5-methylenebarbituric acid derivatives (2) seems to
offer a useful access to 1 [3] in addition to methods
mentioned formerly [1, 4]. Recently, we reported on
the synthesis of the zwitterionic pyridinium compound
3 and its substitution reactions [5].
Surprisingly, it has now been found that the reac-
tion of 3 with N,N-dimethylaniline does not stop with
the formation of the zwitterionic compound 4 and its
anion 5. Apparently, the enolate 5 is sufficiently nu-
cleophilic to attack a second molecule of 3 to give the
final product 6 in good yield (Scheme 1).
Scheme 1.
The crystal structure analysis of 6 (Table 1, Fig. 1)
reveals the presence of a central barbituric ring con-
nected to both an aniline and an additional barbi-
turic ring by methylene bridges. Interestingly, the “ter-
minal” barbituric ring also adopts a diketo structure
which underlines the C-basicity of the enolate frag-
ment. Bond lengths and angles are in the expected
range (see Table 2).
pound for the synthesis of barbituric acid derivatives 1.
We will continue our investigations about pyridine
substitution in 3 and report on our results in due
course.
Experimental Section
All experiments were performed in purified solvents un-
der argon. The pyridine adduct 3 was obtained according to
In summary, our results confirm the suitability of
the easily prepared pyridine adduct 3 as starting com- a published procedure [5].
c
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100
Note
˚
Table 1. Crystal data and structure refinement for Table 2. Selected bond lengths (A) and angles (deg) for
C22H27N5O6 (6).
C22H27N5O6 (6).
Empirical formula
Formula weight, g mol−1
Temperature, K
C22H27N5O6
457.49
173(2)
MoKα ; 0.71073
monoclinic
P21/n
12.1221(9)
9.287(1)
20.090(2)
101.787(6)
2214.1(3)
4
1.37
C(1)–C(6)
C(1)–C(2)
1.503(3)
1.505(3)
1.556(3)
1.209(2)
1.379(2)
1.390(2)
1.205(2)
1.394(2)
1.372(2)
1.216(2)
1.537(2)
1.512(3)
1.514(3)
1.589(3)
1.210(2)
C(14)–N(15)
N(15)–C(16)
C(16)–O(21)
C(16)–N(17)
N(17)–C(18)
C(18)–O(23)
C(24)–C(25)
C(25)–C(26)
C(25)–C(30)
C(26)–C(27)
C(27)–C(28)
C(28)–N(31)
C(28)–C(29)
C(29)–C(30)
1.382(2)
1.381(3)
1.208(2)
1.393(3)
1.371(2)
1.215(2)
1.507(3)
1.390(3)
1.391(3)
1.383(3)
1.404(3)
1.377(3)
1.402(3)
1.384(3)
C(1)–C(12)
C(2)–O(7)
C(2)–N(3)
N(3)–C(4)
C(4)–O(9)
C(4)–N(5)
N(5)–C(6)
C(6)–O(11)
C(12)–C(13)
C(13)–C(18)
C(13)–C(14)
C(13)–C(24)
C(14)–O(19)
˚
Wavelength; λ, A
Crystal system
Space group
˚
a, A
˚
b, A
˚
c, A
β, deg
3
˚
V, A
Z
Density, g cm−3
µ(MoKα ), mm−1
F(000), e
0.1
968
Θ range for data collection, deg
3.09 – 26.36
15, 11, 25
30767 / 4515 / 0.098
Full-matrix least-squares on F2
4515 / 0 / 407
0.0520 / 0.1048
0.0677 / 0.1111
1.151
C(13)–C(12)–C(1)
C(12)–C(13)–C(24)
C(25)–C(24)–C(13)
116.4(2)
106.8(2)
115.1(2)
C(6)–C(1)–C(2)
C(6)–C(1)–C(12) 111.6(2)
C(2)–C(1)–C(12) 106.1(2)
115.1(2)
hkl ranges
Reflections collect. / indep. / Rint
Refinement method
Data / restraints / parameters
R1 / wR2 [I ≥ 2 σ(I)]
R1 / wR2 (all data)
Goodness-of-fit on F2
C(33)–N(31)–C(32) 117.6(2)
−3
˚
∆ρ (max / min), e A
+0.267 / −0.207
C
H
22 27
N O (6)
5 6
To a solution of 3 (2.2 g, 8.9 mmol) in dichloromethane
(20 mL) N,N-dimethylaniline (0.62 g, 4.9 mmol) was added.
The mixture was stirred at r. t. for 24 h. The solvent was re-
moved in vacuo to give 0.79 g (70 %) 6 after recrystallization
from dichloromethane/diethyl ether. – 1H NMR (CDCl3):
δ = 2.75 (s, 2 H, 4Ph-CH2), 2.83 (s, 6 H, NMe2), 2.95 (s,
2 H, 5ꢀ-CH2), 3.01 (s, 6 H, 1ꢀ,3ꢀ-CH3), 3.15 (s, 6 H, 1,3-
CH3), 3.65 (s, 1 H, 5ꢀ-H), 6.48 – 6.69 (m, 4 H, C6H4). –
Fig. 1. Molecular structure of C22H27N5O6 (6) in the crystal.
CCDC 743774 contains the supplementary crystallo-
graphic data for this paper. These data can be obtained free
of charge from The Cambridge Crystallographic Data Centre
via www.ccdc.cam.ac.uk/data request/cif.
13C NMR (CDCl3): δ = 28.2 (1,3-CH3), 28.5 (1ꢀ,3ꢀ-CH3),
ꢀ
33.7 (4Ar-CH2), 40.3 (NMe2), 44.6 (C5 ), 49.5 C5), 56.1 (5ꢀ-
CH2), 111.8 (C2,6Ar), 119.9ꢀ (C4Ar), 129.7 (C3,5Ar), 150.3
ꢀ
ꢀ
(C1Ph), 150.6 (C2), 151.2 (C2 ), 168.3 (C4 ,6 ), 170.9 (C4,6). –
MS (FAB): m/z (%) = 457 (11) [M–H]+, 288 (15) [M–
BCH3]+. – Elemental analysis for C22H27N5O6 (457.48):
Acknowledgement
Financial support by the Deutsche Forschungsgemein-
calcd. C 57.76, H 5.95, N 15.31; found C 57.41, H 6.19, schaft and the Higher Council of Science and Technology
N 15.12.
of Jordan is gratefully acknowledged.
[3] B. S. Jursic, D. M. Neumann, Tetrahedron Lett. 2001,
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[4] For more recent results, see C. Lo¨fberg, R. Grigg,
A. Keep, A. Derrick, V. Sridharan, C. Kilner, J. Chem.
Soc., Chem. Commun. 2006, 5000, and refs. cited
therein.
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K. Undheim, T. Bennecke, A. R. Katritzky, C. W. Rees,
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