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organic papers
Acta Crystallographica Section E

Structure Reports Online
ISSN 1600-5368

1-[(4-Chlorobenzoyl)methyl]-4,6-dimethyl2(1H)-pyrimidone

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

In the title molecule, C14H13ClN2O2, all bond lengths and angles show normal values. The mean planes of the heterocyclic ring and the carbonyl group make a dihedral angle of 81.38 (5) .

Received 3 July 2006 Accepted 8 August 2006

Comment
We have previously described the crystal structures of a series of N-phenacyl-2-pyridones (Albov et al., 2004a,b, 2005) and the structure of N-phenacyl-2-pyrimidone (Rybakov et al., 2006). In this communication, we report the synthesis and crystal structure of a homologue of these compounds, the title compound, (2), N-phenacyl-4,6-dimethyl-2-pyrimidone.

Key indicators Single-crystal X-ray study T = 293 K ° Mean (C­C) = 0.002 A R factor = 0.036 wR factor = 0.086 Data-to-parameter ratio = 15.4 For details of how these key indicators were automatically derived from the article, see http://journals.iucr.org/e.

Interestingly, in the study of the phenacylation of sterically hindered 4,6-dimethylpyrimidone, only the N-isomer has been isolated, in poor yield (Ivanov & Reznik, 1983; Buchan et al., 1978). We have found that, in the reaction of 4,6-dimethyl-2pyrimidone, (1), with phenacyl bromide in the presence of K2CO3, a mixture of two products is formed, namely Nphenacylpyrimidone (N-isomer) and O-phenacylpyrimidone (O-isomer). With the goal of decreasing the yield of the Oisomer, we have used the sodium salt in the reaction with pchlorophenacyl bromide. The only product observed in this reaction was the title compound, (2). In compound (2) (Fig. 1), all bond lengths and angles show normal values (Cambridge Structural Database; Version 5.27; Allen, 2002). In the pyrimidone (P) ring, N1/C2/N3/C4 C6, the single and double bonds alternate (Table 1), allowing some degree of conjugation. The mean planes of P and the carbonyl group C7/C8/O8/C9 make a dihedral angle of 81.38 (5) . The torsion angle O8 C8 C9 C14 = 4.1 (3) indicates conjugation with the benzoyl fragment.

Experimental
4,6 Dimethyl 2 pyrimidone hydrochloride (5 g, 0.031 mol) and NaOH (1.25 g 0.031 mol) were dissolved in water (30 ml), stirred for 5 min and evaporated in vacuo. The residue was dissolved in CHCl3 (50 ml), refluxed for 5 min and filtered. The filtrate was evaporated in vacuo to give the dimethylpyrimidone as the free base (3.8 g, 100%). The resulting 4,6 dimethyl 2 pyrimidone was added to a solution of sodium methylate (prepared by dissolving 0.031 mol sodium in 15 ml
2

# 2006 International Union of Crystallography All rights reserved

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doi:10.1107/S1600536806031199

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organic papers
Table 1
° Selected geometric parameters (A, ).
N1--C6 N1--C2 N1--C7 C2--O2 C2--N3 C6--N1--C2 C6--N1--C7 C2--N1--C7 O2--C2--N3 O2--C2--N1 N3--C2--N1 1.3607 1.4116 1.4648 1.2210 1.3645 122.06 123.33 114.45 123.27 118.50 118.23 (18) (19) (16) (18) (18) (12) (13) (12) (16) (14) (14) N3--C4 C4--C5 C4--C41 C5--C6 C6--C61 C4--N3--C2 N3--C4--C5 C6--C5--C4 C5--C6--N1 N1--C7--C8 1.307 (2) 1.402 (2) 1.502 (2) 1.3586 (19) 1.493 (2) 119.31 123.56 118.71 118.13 110.70 (15) (14) (15) (15) (12)

Figure 1
The structure of the title compound, showing the atom numbering scheme. Displacement ellipsoids are drawn at the 50% probability level.

of anhydrous methanol), and the mixture was stirred for 30 min. The resulting precipitate of the sodium salt of dimethylpyrimidone was filtered off (4.40 g, 98%). This sodium salt of 2 pyrimidone (1.5 g, 0.01 mol) was suspended in benzene (10 ml). p Chlorophenacyl bromide was then added (1.9 g, 0.0067 mol) and the mixture was stirred for 6 d at room temperature. The precipitate which formed was filtered off, and washed with water and then with diethyl ether. The product was isolated by suction and recrystallized from acet onitrile (yield 33%, m.p. 445 447 K). Crystal data
C14H13ClN2O2 Mr = 276.71 Monoclinic, P21 =n ° a = 7.1975 (8) A ° b = 9.3817 (10) A ° c = 19.422 (3) A  = 92.314 (9) ° V = 1310.4 (3) A3 Z=4 Dx = 1.403 Mg mю3 Cu K radiation = 2.58 mmю1 T = 293 (2) K Prism, colourless 0.2 б 0.2 б 0.2 mm

° All H atoms were positioned geometrically (C H 0.93 0.97 A) and refined using a riding model, with Uiso(H) 1.2Ueq (1.5Ueq for CH3) of the parent atom. Data collection: CAD 4 EXPRESS; cell refinement: CAD 4 EXPRESS (Enraf Nonius, 1994); 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 for the use of the Cambridge Structural Database.

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). Crystallogr. Rep. 50, 660 664. Allen, F. H. (2002). Acta Cryst. B58, 380 388. Buchan, R., Frazer, M. & Shand, C. (1978). J. Org. Chem. 43, 3544 3547. Enraf Nonius (1994). CAD-4 Software. Version 5.0. Enraf Nonius, Delft, The Netherlands. Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565. Farrugia, L. J. (1999). J. Appl. Cryst. 32, 837 838. Harms, K. & Wocadlo, S. (1995). XCAD4. University of Marburg, Germany. Ivanov, V. B., Reznik, V. S. & Efremov, Yu. Ya. (1983). Bull. Acad. Sci. USSR Div. Chem. Sci. (Engl. Transl.), 32, 2130 2134. Rybakov, V. B., Tsisevich, A. A. V., Nikitin, K. L., Alifanov, V. & Babaev, E. V. (2006). Acta Cryst. E62, o2546 o2547. Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of Ё Gottingen, Germany.

Data collection
Enraf Nonius CAD-4 diffractometer ! scans Absorption correction: none 2760 measured reflections 2683 independent reflections 1907 reflections with I > 2 (I) Rint = 0.090 max = 74.9 1 standard reflections frequency: 60 min intensity decay: 4%

Refinement
Refinement on F 2 R[F 2 > 2 (F 2)] = 0.036 wR(F 2) = 0.086 S = 0.96 2683 reflections 174 parameters H-atom parameters constrained w = 1/[ 2(Fo2) + (0.0422P)2] where P = (Fo2 + 2Fc2)/3 (а/ )max = 0.003 ° аmax = 0.12 e Aю3 ° аmin = ю0.14 e Aю3

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