Ethyl 6-amino-5-cyano-2-methyl-4-propyl-4H-pyran-3-carboxyl­ate

Yu, Q.-D.; Li, K.-X.; Liu, Y.-Y.

doi:10.1107/S1600536809043748

organic compounds

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ISSN: 2056-9890

Volume 65| Part 11| November 2009| Page o2862

https://doi.org/10.1107/S1600536809043748

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Ethyl 6-amino-5-cyano-2-methyl-4-propyl-4H-pyran-3-carboxylate

Qun-Di Yu,^a Ke-Xin Li ^b ^* and Yun-Yu Liu ^c

^aFood Science and Pharmacy College, Zhejiang Ocean University, Zhoushan 316000, People's Republic of China, ^bPeople's Hospital of Jilin Province, Changchun 130021, People's Republic of China, and ^cDepartment of Chemistry, Northeast Normal University, Changchun 130024, People's Republic of China
^*Correspondence e-mail: yunyuliu888@yahoo.com.cn

(Received 22 October 2009; accepted 22 October 2009; online 28 October 2009)

The pyran ring of the title compound, C₁₃H₁₈N₂O₃, is almost planar (r.m.s. deviation = 0.059 Å). The crystal packing is stabilized by N—H⋯O and N—H⋯N hydrogen bonds.

Related literature

Ethyl 6-amino-5-cyano-2-methyl-4-propyl-4H-pyran-3-carboxylate and its derivatives are widely utilized as organic intermediates, see: Liang et al. (2009 ).

Experimental

Crystal data

C₁₃H₁₈N₂O₃
M_r = 250.15
Triclinic, $[P \overline 1]$
a = 8.1172 (9) Å
b = 8.7956 (9) Å
c = 11.2877 (19) Å
α = 106.082 (12)°
β = 107.274 (12)°
γ = 103.315 (9)°
V = 695.20 (19) Å³
Z = 2
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 293 K
0.25 × 0.23 × 0.20 mm

Data collection

Bruker SMART APEX CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 1998 ) T_min = 0.65, T_max = 0.87
5049 measured reflections
2826 independent reflections
1577 reflections with I > 2σ(I)
R_int = 0.023

Refinement

R[F² > 2σ(F²)] = 0.046
wR(F²) = 0.129
S = 0.89
2826 reflections
172 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.13 e Å⁻³
Δρ_min = −0.22 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2A⋯O1ⁱ	0.805 (18)	2.088 (19)	2.881 (2)	168.2 (17)
N2—H2B⋯N1ⁱⁱ	0.85 (2)	2.21 (2)	3.035 (3)	164.4 (17)
Symmetry codes: (i) x-1, y, z; (ii) -x-1, -y-1, -z+1.

Data collection: SMART (Bruker, 1998); cell refinement: SAINT (Bruker, 1998); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536809043748/bt5109sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536809043748/bt5109Isup2.hkl

checkCIF report

Comment top

Ethyl 6-amino-5-cyano-2-methyl-4-propyl-4H-pyran-3-carboxylate and its derivatives are widely utilized as organic intermediates (Liang et al., 2009).

The pyran ring of the title compound, C₁₃H₁₈N₂O₃, is almost planar (r.m.s. deviation 0.059Å). The crystal packing is stabilized by N-H···O and N-H···N hydrogen bonds.

Related literature top

Ethyl 6-amino-5-cyano-2-methyl-4-propyl-4H-pyran-3-carboxylate and its derivatives are widely utilized as organic intermediates, see: Liang et al. (2009).

Experimental top

A mixture of butyraldehyde (1.0 mmol), malononitrile (1.0 mmol) and acetyl acetate (1.0 mmol) was dissolved in 5 mL dimethylformamide and catalytic amount of piperidine (0.2 mmol) was added at room temperature under stirring. After 2h, the reaction mixture was poured into water and extracted with CH₂Cl₂. The combined organic phase was washed with water, dried over MgSO₄, filtered and concentrated in vacuo. The crude product was purified by silica column chromatography. Yield: 87%. Pure product was dissolved in a mixture of petroleum ether. The single-crystals were obtained by slow evaporation of the solvents.

Structure description top

Ethyl 6-amino-5-cyano-2-methyl-4-propyl-4H-pyran-3-carboxylate and its derivatives are widely utilized as organic intermediates (Liang et al., 2009).

The pyran ring of the title compound, C₁₃H₁₈N₂O₃, is almost planar (r.m.s. deviation 0.059Å). The crystal packing is stabilized by N-H···O and N-H···N hydrogen bonds.

Ethyl 6-amino-5-cyano-2-methyl-4-propyl-4H-pyran-3-carboxylate and its derivatives are widely utilized as organic intermediates, see: Liang et al. (2009).

Computing details top

Data collection: SMART (Bruker, 1998); cell refinement: SAINT (Bruker, 1998); data reduction: SAINT (Bruker, 1998); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

Fig. 1. The structure of the title compound, showing the atomic numbering scheme. Displacement ellipsoids are drawn at the 30% probability level.

Ethyl 6-amino-5-cyano-2-methyl-4-propyl-4H-pyran-3-carboxylate top

Crystal data top

C₁₃H₁₈N₂O₃	Z = 2
M_r = 250.15	F(000) = 268
Triclinic, P1	D_x = 1.195 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.1172 (9) Å	Cell parameters from 2826 reflections
b = 8.7956 (9) Å	θ = 3.0–26.4°
c = 11.2877 (19) Å	µ = 0.09 mm⁻¹
α = 106.082 (12)°	T = 293 K
β = 107.274 (12)°	Block, colorless
γ = 103.315 (9)°	0.25 × 0.23 × 0.20 mm
V = 695.20 (19) Å³

Data collection top

Bruker APEX CCD area-detector diffractometer	2826 independent reflections
Radiation source: fine-focus sealed tube	1577 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.023
φ and ω scans	θ_max = 26.4°, θ_min = 2.6°
Absorption correction: multi-scan (SADABS; Bruker, 1998)	h = −10→10
T_min = 0.65, T_max = 0.87	k = −10→10
5049 measured reflections	l = −13→14

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.046	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.129	H atoms treated by a mixture of independent and constrained refinement
S = 0.89	w = 1/[σ²(F_o²) + (0.0757P)²] where P = (F_o² + 2F_c²)/3
2826 reflections	(Δ/σ)_max < 0.001
172 parameters	Δρ_max = 0.13 e Å⁻³
0 restraints	Δρ_min = −0.22 e Å⁻³

Crystal data top

C₁₃H₁₈N₂O₃	γ = 103.315 (9)°
M_r = 250.15	V = 695.20 (19) Å³
Triclinic, P1	Z = 2
a = 8.1172 (9) Å	Mo Kα radiation
b = 8.7956 (9) Å	µ = 0.09 mm⁻¹
c = 11.2877 (19) Å	T = 293 K
α = 106.082 (12)°	0.25 × 0.23 × 0.20 mm
β = 107.274 (12)°

Data collection top

Bruker APEX CCD area-detector diffractometer	2826 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 1998)	1577 reflections with I > 2σ(I)
T_min = 0.65, T_max = 0.87	R_int = 0.023
5049 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.046	0 restraints
wR(F²) = 0.129	H atoms treated by a mixture of independent and constrained refinement
S = 0.89	Δρ_max = 0.13 e Å⁻³
2826 reflections	Δρ_min = −0.22 e Å⁻³
172 parameters

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > 2sigma(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
C1	−0.2429 (2)	−0.09571 (19)	0.63342 (17)	0.0444 (4)
C2	−0.1346 (2)	−0.18666 (19)	0.61071 (16)	0.0428 (4)
C3	−0.2165 (2)	−0.3640 (2)	0.55184 (18)	0.0507 (5)
C4	0.0703 (2)	−0.10825 (19)	0.65363 (16)	0.0416 (4)
H4	0.1012	−0.1530	0.5765	0.050*
C5	0.1778 (2)	−0.1557 (2)	0.76684 (17)	0.0513 (5)
H5A	0.1418	−0.2774	0.7362	0.062*
H5B	0.3075	−0.1117	0.7850	0.062*
C6	0.1500 (3)	−0.0922 (3)	0.8948 (2)	0.0716 (6)
H6A	0.0195	−0.1271	0.8756	0.086*
H6B	0.1976	0.0298	0.9305	0.086*
C7	0.2423 (4)	−0.1545 (3)	1.0004 (2)	0.1038 (9)
H7A	0.2186	−0.1102	1.0791	0.156*
H7B	0.3723	−0.1175	1.0223	0.156*
H7C	0.1945	−0.2753	0.9666	0.156*
C8	0.0021 (2)	0.1608 (2)	0.70345 (17)	0.0446 (4)
C9	0.1207 (2)	0.08115 (19)	0.69043 (16)	0.0404 (4)
C10	0.0223 (3)	0.3431 (2)	0.7354 (2)	0.0670 (6)
H10A	−0.0868	0.3524	0.6792	0.101*
H10B	0.1258	0.3989	0.7199	0.101*
H10C	0.0409	0.3947	0.8274	0.101*
C11	0.3091 (2)	0.1666 (2)	0.70545 (18)	0.0466 (4)
C12	0.5617 (3)	0.4184 (3)	0.7863 (2)	0.0737 (6)
H12A	0.5646	0.4016	0.6984	0.088*
H12B	0.6491	0.3749	0.8326	0.088*
C13	0.6091 (4)	0.5982 (3)	0.8618 (3)	0.1117 (9)
H13A	0.7300	0.6584	0.8713	0.168*
H13B	0.6061	0.6135	0.9486	0.168*
H13C	0.5222	0.6403	0.8149	0.168*
N2	−0.4192 (2)	−0.1503 (2)	0.61418 (18)	0.0606 (5)
N1	−0.2822 (2)	−0.5075 (2)	0.50412 (19)	0.0763 (6)
O3	−0.17565 (15)	0.07590 (13)	0.68500 (12)	0.0530 (3)
O1	0.39733 (18)	0.09129 (16)	0.65942 (14)	0.0694 (4)
O2	0.37809 (16)	0.33123 (15)	0.77399 (14)	0.0612 (4)
H2A	−0.472 (2)	−0.083 (2)	0.6160 (17)	0.055 (5)*
H2B	−0.485 (3)	−0.253 (3)	0.585 (2)	0.062 (6)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0435 (10)	0.0357 (9)	0.0503 (11)	0.0118 (8)	0.0178 (8)	0.0123 (8)
C2	0.0427 (10)	0.0356 (9)	0.0466 (10)	0.0149 (8)	0.0133 (8)	0.0131 (8)
C3	0.0410 (10)	0.0451 (11)	0.0606 (12)	0.0174 (9)	0.0140 (9)	0.0157 (9)
C4	0.0439 (10)	0.0366 (9)	0.0449 (10)	0.0182 (8)	0.0168 (8)	0.0129 (7)
C5	0.0490 (11)	0.0426 (10)	0.0593 (12)	0.0179 (8)	0.0138 (9)	0.0205 (9)
C6	0.0846 (16)	0.0705 (14)	0.0584 (13)	0.0299 (12)	0.0213 (11)	0.0261 (11)
C7	0.130 (2)	0.109 (2)	0.0662 (15)	0.0379 (18)	0.0184 (15)	0.0482 (16)
C8	0.0421 (10)	0.0380 (9)	0.0533 (11)	0.0135 (8)	0.0195 (8)	0.0152 (8)
C9	0.0412 (10)	0.0380 (9)	0.0441 (10)	0.0155 (8)	0.0161 (8)	0.0173 (8)
C10	0.0593 (13)	0.0393 (10)	0.1052 (17)	0.0212 (9)	0.0362 (12)	0.0222 (11)
C11	0.0453 (10)	0.0486 (11)	0.0552 (11)	0.0215 (9)	0.0197 (9)	0.0281 (9)
C12	0.0484 (12)	0.0710 (14)	0.0989 (17)	0.0079 (11)	0.0285 (12)	0.0374 (13)
C13	0.0887 (19)	0.0724 (17)	0.134 (3)	−0.0179 (14)	0.0439 (18)	0.0169 (17)
N2	0.0453 (10)	0.0414 (10)	0.0917 (13)	0.0153 (9)	0.0289 (9)	0.0167 (9)
N1	0.0583 (11)	0.0403 (10)	0.1089 (15)	0.0124 (9)	0.0212 (10)	0.0126 (10)
O3	0.0443 (7)	0.0348 (6)	0.0765 (9)	0.0148 (6)	0.0265 (6)	0.0115 (6)
O1	0.0578 (9)	0.0646 (9)	0.1057 (12)	0.0336 (7)	0.0447 (8)	0.0355 (8)
O2	0.0470 (7)	0.0474 (8)	0.0829 (10)	0.0073 (6)	0.0285 (7)	0.0184 (7)

Geometric parameters (Å, º) top

C1—N2	1.329 (2)	C8—C9	1.333 (2)
C1—C2	1.350 (2)	C8—O3	1.3862 (19)
C1—O3	1.3638 (19)	C8—C10	1.501 (2)
C2—C3	1.415 (2)	C9—C11	1.476 (2)
C2—C4	1.512 (2)	C10—H10A	0.9600
C3—N1	1.145 (2)	C10—H10B	0.9600
C4—C9	1.522 (2)	C10—H10C	0.9600
C4—C5	1.540 (2)	C11—O1	1.2122 (18)
C4—H4	0.9800	C11—O2	1.326 (2)
C5—C6	1.502 (3)	C12—O2	1.456 (2)
C5—H5A	0.9700	C12—C13	1.467 (3)
C5—H5B	0.9700	C12—H12A	0.9700
C6—C7	1.517 (3)	C12—H12B	0.9700
C6—H6A	0.9700	C13—H13A	0.9600
C6—H6B	0.9700	C13—H13B	0.9600
C7—H7A	0.9600	C13—H13C	0.9600
C7—H7B	0.9600	N2—H2A	0.805 (18)
C7—H7C	0.9600	N2—H2B	0.85 (2)

N2—C1—C2	128.59 (16)	C9—C8—C10	130.81 (16)
N2—C1—O3	110.12 (13)	O3—C8—C10	107.27 (12)
C2—C1—O3	121.28 (15)	C8—C9—C11	123.41 (14)
C1—C2—C3	117.85 (15)	C8—C9—C4	122.47 (15)
C1—C2—C4	122.94 (14)	C11—C9—C4	114.08 (12)
C3—C2—C4	119.09 (12)	C8—C10—H10A	109.5
N1—C3—C2	179.8 (2)	C8—C10—H10B	109.5
C2—C4—C9	109.31 (11)	H10A—C10—H10B	109.5
C2—C4—C5	111.67 (13)	C8—C10—H10C	109.5
C9—C4—C5	112.78 (13)	H10A—C10—H10C	109.5
C2—C4—H4	107.6	H10B—C10—H10C	109.5
C9—C4—H4	107.6	O1—C11—O2	121.58 (16)
C5—C4—H4	107.6	O1—C11—C9	122.36 (16)
C6—C5—C4	114.61 (13)	O2—C11—C9	116.06 (13)
C6—C5—H5A	108.6	O2—C12—C13	107.97 (17)
C4—C5—H5A	108.6	O2—C12—H12A	110.1
C6—C5—H5B	108.6	C13—C12—H12A	110.1
C4—C5—H5B	108.6	O2—C12—H12B	110.1
H5A—C5—H5B	107.6	C13—C12—H12B	110.1
C5—C6—C7	113.67 (18)	H12A—C12—H12B	108.4
C5—C6—H6A	108.8	C12—C13—H13A	109.5
C7—C6—H6A	108.8	C12—C13—H13B	109.5
C5—C6—H6B	108.8	H13A—C13—H13B	109.5
C7—C6—H6B	108.8	C12—C13—H13C	109.5
H6A—C6—H6B	107.7	H13A—C13—H13C	109.5
C6—C7—H7A	109.5	H13B—C13—H13C	109.5
C6—C7—H7B	109.5	C1—N2—H2A	117.1 (13)
H7A—C7—H7B	109.5	C1—N2—H2B	124.7 (13)
C6—C7—H7C	109.5	H2A—N2—H2B	117.0 (18)
H7A—C7—H7C	109.5	C1—O3—C8	120.17 (11)
H7B—C7—H7C	109.5	C11—O2—C12	116.81 (13)
C9—C8—O3	121.91 (14)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···O1ⁱ	0.805 (18)	2.088 (19)	2.881 (2)	168.2 (17)
N2—H2B···N1ⁱⁱ	0.85 (2)	2.21 (2)	3.035 (3)	164.4 (17)

Symmetry codes: (i) x−1, y, z; (ii) −x−1, −y−1, −z+1.

Experimental details

Crystal data
Chemical formula	C₁₃H₁₈N₂O₃
M_r	250.15
Crystal system, space group	Triclinic, P1
Temperature (K)	293
a, b, c (Å)	8.1172 (9), 8.7956 (9), 11.2877 (19)
α, β, γ (°)	106.082 (12), 107.274 (12), 103.315 (9)
V (Å³)	695.20 (19)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.25 × 0.23 × 0.20

Data collection
Diffractometer	Bruker APEX CCD area-detector
Absorption correction	Multi-scan (SADABS; Bruker, 1998)
T_min, T_max	0.65, 0.87
No. of measured, independent and observed [I > 2σ(I)] reflections	5049, 2826, 1577
R_int	0.023
(sin θ/λ)_max (Å⁻¹)	0.625

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.046, 0.129, 0.89
No. of reflections	2826
No. of parameters	172
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.13, −0.22

Computer programs: SMART (Bruker, 1998), SAINT (Bruker, 1998), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···O1ⁱ	0.805 (18)	2.088 (19)	2.881 (2)	168.2 (17)
N2—H2B···N1ⁱⁱ	0.85 (2)	2.21 (2)	3.035 (3)	164.4 (17)

Symmetry codes: (i) x−1, y, z; (ii) −x−1, −y−1, −z+1.

Acknowledgements

We thank Zhejiang Ocean University, the People's Hospital of Jilin Province and the Science Foundation for Young Teachers of Northeast Normal University (No. 20080305) for support.

References

Bruker (1998). SMART, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Liang, F., Cheng, X., Liu, J. & Liu, Q. (2009). Chem. Commun. pp. 3636–3538. Web of Science CSD CrossRef Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar