Документ взят из кэша поисковой машины. Адрес оригинального документа : http://www.chem.msu.ru/eng/misc/babaev/papers/118e.pdf Дата изменения: Fri Jan 21 15:32:24 2011 Дата индексирования: Sat Feb 12 03:14:31 2011 Кодировка:

organic papers
Acta Crystallographica Section E

Structure Reports Online
ISSN 1600-5368

1-(4-Chlorobenzoylmethyl)pyrimidin2(1H)-one

Victor B. Rybakov,* Alexander A. Tsisevich, Kirill V.Nikitin, Vadim L.Alifanov and Eugene V. Babaev
Department of Chemistry, Moscow State University, 119992 Moscow, Russian Federation Correspondence e-mail: rybakov20021@yandex.ru

The title compound, C12H9ClN2O2, was synthesized and characterized by 1H NMR and IR spectrocopy and X-ray diffraction techniques. The chlorobenzoyl fragment in the structure is almost flat, whereas the carbonyl group is almost perpendicular to the pyrimidine ring plane.

Received 24 April 2006 Accepted 22 May 2006

Comment
We have previously described the crystal structures of a series of N-phenacyl-2-pyridones (Albov et al., 2004a,b, 2005). We report here the synthesis and crystal structure of their azaanalog, (2). In contrast to well investigated reactions of pyridones with -halogenoketones, analogous reactions for pyrimidones have been little studied. There are only a few examples, namely the reaction of (1) with the acetal of bromoacetaldehyde (Holy et al., 1984) or with chloroacetic acid derivatives (Gefenas & Vainilavichus, 2003) and phenacylation of the 5-chloro derivative of (1) (Benneche & Gandersen, 1988). In all of these cases, the products of Nalkylation were exclusively observed. Interestingly, in the study of the phenacylation of sterically hindered 4,6dimethylpyrimidone, only the N-isomers have been isolated (Ivanov et al., 1983; Buchan et al., 1978). Usually these reactions are performed in aprotic bipolar solvents in the presense of bases, so that the alkylated species has been the pyrimidone anion.

Key indicators Single-crystal X-ray study T = 293 K ° Mean (C­C) = 0.004 A R factor = 0.054 wR factor = 0.161 Data-to-parameter ratio = 15.0 For details of how these key indicators were automatically derived from the article, see http://journals.iucr.org/e.

# 2006 International Union of Crystallography All rights reserved

We have found that reaction of (1) with p-chlorophenacyl bromide in the presense of K2CO3 in acetone yields the title compound, (2). The 1H NMR spectra were useless for distinguishing between O-and N-isomers. In the IR spectrum of (2), two C O peaks were observed, one for the N C O fragment of pyrimidone and another for the carbonyl group, thus clearly confirming selective N-alkylation (in the case of Ophenacylation no amide peak would be observed). The structure of the N-isomer was finally confirmed by X-ray crystallographic analysis. In the pyrimidone ring of (2), the single and double bonds alternate (Table 1), though allowing some degree of conjugation. In the Cambridge Structural Database (CSD; Version 5.27; Allen, 2002), we found only one structure with the pyrimidone (2) fragment, namely the parent pyrimidone (1) (Furberg & Solbakk, 1970) with the same distribution of bond lengths. In the structure of (2), the dihedral angle between the
2

o2546

Rybakov et al.



C12H9ClN2O

doi:10.1107/S1600536806018927

Acta Cryst. (2006). E62, o2546 o2547


organic papers
Table 1
N1--C6 N1--C2 N1--C7 C2--O2 C2--N3 N3--C4 C4--C5 C5--C6 C7--C8 C6--N1--C2 C6--N1--C7 C2--N1--C7 O2--C2--N3 O2--C2--N1 N3--C2--N1 C4--N3--C2 N3--C4--C5 C6--C5--C4 C5--C6--N1 N1--C7--C8 O8--C8--C9

° Selected geometric parameters (A, ).
1.353 1.399 1.455 1.226 1.364 1.307 1.397 1.341 1.514 (3) (3) (3) (3) (3) (3) (3) (4) (3) C8--O8 C8--C9 C9--C10 C9--C14 C10--C11 C11--C12 C12--C13 C12--Cl12 C13--C14 O8--C8--C7 C9--C8--C7 C10--C9--C14 C10--C9--C8 C14--C9--C8 C11--C10--C9 C12--C11--C10 C11--C12--C13 C11--C12--Cl12 C13--C12--Cl12 C14--C13--C12 C13--C14--C9 1.213 1.477 1.395 1.396 1.382 1.379 1.384 1.742 1.371 (3) (3) (3) (3) (3) (3) (4) (2) (4)

Figure 1
The structure of the title compound, showing the atom numbering scheme. Displacement ellipsoids are drawn at the 50% probability level, with H atoms shown as spheres of arbitrary radius.

pyrimidone ring and the C7/C8/O8/C9 unit is 81.57 (8) . The O8 C8 C9 C14 torsion angle of ю4.2 (2) indicates conjugation in the benzoyl fragment.

121.49 (19) 120.52 (19) 117.84 (19) 122.8 (2) 119.7 (2) 117.53 (19) 119.42 (19) 124.3 (2) 116.6 (2) 120.5 (2) 111.92 (19) 122.0 (2)

119.5 (2) 118.47 (19) 118.8 (2) 122.9 (2) 118.3 (2) 120.3 (2) 119.4 (2) 121.4 (2) 119.3 (2) 119.22 (19) 118.8 (2) 121.3 (2)

Experimental
The hydrochloride of (1) (26.5 g; 0.2 mol) was suspended in 500 ml of dry acetone. A solution of 0.1 mol of p chlorophenacyl bromide in 100 ml acetone and 0.4 mol K2CO3 was added with stirring. The reaction mixture was stirred for 2 d at room temperature, and then the solvent was evaporated under vacuum. The residue was washed with water and then with ethyl acetate The product was isolated by suction and recrystallized from acetonitrile. (yield 95%, m.p. 497 499 K). 1H NMR (DMSO d6/TMS): J(Hz) 8.57 (m, 1H, H 6), 8.02 8.16 (m, 3H, 2H of p ClPh, H 4), 7.57 (m, 2H, p ClPh), 6.42 (m, 1H, H 5), 5.44 (s, 2H, NCH2). IR (nujol) CO, cmю1 1695, 1615. Analysis calculated for C12H9ClN2O2: C 57.96, H 3.65, N 11.27%; found: C 57.67, H 3.41, N 11.29%. Crystal data
C12H9ClN2O2 Mr = 248.66 Monoclinic, P21 =n ° a = 10.2191 (10) A ° b = 10.8421 (14) A ° c = 11.3449 (15) A  = 115.065 (11) ° V = 1138.6 (3) A3 Z=4 Dx = 1.451 Mg mю3 Cu K radiation = 2.91 mmю1 T = 293 (2) K Prism, colourless 0.2 б 0.2 б 0.2 mm

° All H atoms were refined using a riding model, with C H 0.93 A ° and Uiso(H) 1.2Ueq(C) for aromatic H atoms C H 0.97 A and ° Uiso(H) 1.2Ueq(C) for CH2 H atoms, and C H 0.96 A and Uiso(H) 1.5Ueq(C) for CH3 H atoms. Data collection: CAD 4 EXPRESS (Enraf Nonius, 1994); cell refinement: CAD 4 EXPRESS; data reduction: XCAD4 (Harms & Wocadlo, 1995); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP 3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).

The authors are indebted to the Russian Foundation for Basic Research for covering the licence fee to use the CSD.

References
Albov, D. V., Rybakov, V. B., Babaev, E. V. & Aslanov, L. A. (2004a). Acta Cryst. E60, o1098 o1099. Albov, D. V., Rybakov, V. B., Babaev, E. V. & Aslanov, L. A. (2004b). Acta Cryst. E60, o1952 o1953. Albov, D. V., Rybakov, V. B., Babaev, E. V. & Aslanov, L. A. (2005). Cryst. Rep. 50, 660 664. Allen, H. F. (2002). Acta Cryst. B58, 380 388. Benneche, T. & Gandersen, L. (1988). Acta. Chem. Scand. Ser. B, 42, 384 389. Buchan, R., Frazer, M. & Shand, C. (1978). J. Org. Chem. 43, 3544 3547. Enraf Nonius (1994). CAD-4 EXPRESS. Version 5.1/1.2. Enraf Nonius, Delft, The Netherlands. Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565. Farrugia, L. J. (1999). J. Appl. Cryst. 32, 837 838. Furberg, S. & Solbakk, J. (1970). Acta Chem. Scand. 24, 3230 3236. Gefenas, V. I. & Vainilavichus, V. I. (2003). Chim. Geterotsikl. Soedin. 20, 1429 1430. (In Russian.) Harms, K. & Wocadlo, S. (1995). XCAD4. University of Marburg, Germany. Holy, A., Ludzisa, A. & Votruba, I. (1984). Coll. Czech. Chem. Commun. 50, 393 415. Ivanov, V. B., Reznik, V. S. & Efremov, Yu. Ya. (1983). Bull. Acad. Sci. USSR Div. Chem. Sci. (Engl. Transl.), 32, 2130 2134. Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of Ё Gottingen, Germany.

Data collection
Enraf Nonius CAD-4 diffractometer ! scans Absorption correction: none 2327 measured reflections 2327 independent reflections 1842 reflections with I > 2 (I) max = 77.9 1 standard reflection frequency: 120 min intensity decay: 5%

Refinement
Refinement on F 2 R[F 2 > 2 (F 2)] = 0.054 wR(F 2) = 0.161 S = 1.14 2327 reflections 155 parameters H-atom parameters constrained w = 1/[ 2(Fo2) + (0.0895P)2 + 0.2167P] where P = (Fo2 + 2Fc2)/3 (а/ )max = 0.002 ° аmax = 0.71 e Aю3 ° аmin = ю0.79 e Aю3 Extinction correction: SHELXL97 Extinction coefficient: 0.0192 (19)

Acta Cryst. (2006). E62, o2546 o2547

Rybakov et al.



C12H9ClN2O2

o2547