Ethyl 5-methyl-4-oxo-3-phenyl-2-propyl­amino-3,4-dihydro­thieno[2,3-d]pyrimidine-6-carboxyl­ate

Ai-Hua Zheng; Yan-Mei Ren; Jing Xu

doi:10.1107/S1600536809033595

. 2009 Aug 29;65(Pt 9):o2266. doi: 10.1107/S1600536809033595

Ethyl 5-methyl-4-oxo-3-phenyl-2-propylamino-3,4-dihydrothieno[2,3-d]pyrimidine-6-carboxylate

Ai-Hua Zheng ^a, Yan-Mei Ren ^b, Jing Xu ^a,^*

PMCID: PMC2969942 PMID: 21577661

Abstract

The title compound, C₁₉H₂₁N₃O₃S, was synthesized via the aza-Wittig reaction of functionalized iminophosphorane with phenyl isocyanate under mild conditions. In the molecule, the fused thienopyrimidine ring system is essentially planar, with a maximum deviation of 0.072 (2) Å, and makes a dihedral angle of 60.11 (9)° with the phenyl ring. An intramolecular C—H⋯O hydrogen bond is present. The crystal packing is stabilized by intermolecular N—H⋯O and C—H⋯O hydrogen bonds.

Related literature

For the preparation and biological and pharmaceutical activities of pyrimidinone derivatives, see: Modica et al. (2004 ▶); Panico et al. (2001 ▶). For the biological activity of thienopyrimidine derivatives, see: Ding et al. (2004 ▶).

Experimental

Crystal data

C₁₉H₂₁N₃O₃S
M _r = 371.45
Orthorhombic,
a = 8.1682 (2) Å
b = 14.1247 (3) Å
c = 16.0672 (5) Å
V = 1853.73 (8) Å³
Z = 4
Mo Kα radiation
μ = 0.20 mm⁻¹
T = 298 K
0.16 × 0.12 × 0.10 mm

Data collection

Bruker SMART 4K CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.969, T _max = 0.980
10064 measured reflections
4472 independent reflections
4226 reflections with I > 2σ(I)
R _int = 0.031

Refinement

R[F ² > 2σ(F ²)] = 0.053
wR(F ²) = 0.136
S = 1.13
4472 reflections
241 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.39 e Å⁻³
Δρ_min = −0.37 e Å⁻³
Absolute structure: Flack (1983 ▶), 1861 Freidel pairs
Flack parameter: 0.08 (10)

Data collection: SMART (Bruker, 2001 ▶); cell refinement: SAINT-Plus (Bruker, 2001 ▶); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: PLATON (Spek, 2009 ▶); software used to prepare material for publication: SHELXTL (Sheldrick, 2008 ▶).

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809033595/at2864sup1.cif

e-65-o2266-sup1.cif^{(21KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809033595/at2864Isup2.hkl

e-65-o2266-Isup2.hkl^{(219.1KB, hkl)}

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C6—H6⋯O2ⁱ	0.93	2.58	3.359 (3)	142
C2—H2⋯O2ⁱⁱ	0.93	2.50	3.432 (3)	177
N3—H3A⋯O1ⁱⁱⁱ	0.88 (3)	2.08 (3)	2.863 (3)	147 (3)
C16—H16C⋯O2	0.96	2.31	3.000 (3)	128

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Symmetry codes: (i) Inline graphic ; (ii) ; (iii) .

Acknowledgments

We gratefully acknowledge financial support of this work by the Key Science Research Project of Hubei Provincial Department of Education (No. D20092406) and the Science Research Project of Yunyang Medical College (No. 2007QDJ14).

supplementary crystallographic information

Comment

The derivatives of thienopyrimidine are of great importance because of their remarked biological properties (Ding et al., 2004). We have recently focused on the synthesis of fused heterocyclic systems containing a fused pyrimidinone ring moiety using aza-Wittig reaction. The title compound, may be used as a new precursor for obtaining bioactive molecules and its structure is reported here, Fig.1. The bond lengths and angles are unexceptional. The thienopyrimidinone rings are closer to coplanarity with maximum deviations 0.072 (2)Å and -0.058 (2)Å for C10 and N1, respectively. The phenyl ring is twisted with respect to the pyrimidinone ring, with a dihedral angle of 60.11 (9)°. Intramolecular C—H···O and intermolecular C—H···O, N—H···O hydrogen bonds interactions are present, which stabilize the conformation of the molecule and the crystal structure (Table 1).

Experimental

To a solution of diethyl 5-((phenylimino)methyleneamino)- 3-methylthiophene-2,4-dicarboxylate(3 mmol) in anhydrous dichloromethane (15 ml) was added propan-1-amine (3 mmol). After stirring the reaction mixture for 1 h, the solvent was removed and anhydrous ethanol (10 ml) with several drops of EtONa in EtOH was added. The mixture was stirred for 5 h at room temperature. The solution was concentrated under reduced pressure and the residue was recrystallized from ethanol to give the title compound in a yield of 78%. Crystals suitable for single-crystal X-ray diffraction were obtained by recrystallization from a mixed solvent of ethanol and dichloromethane (1:1 v/v) at room temperature.