tert-Butyl 6-amino-5-cyano-2-(2-meth­oxy­eth­yl)nicotinate

Yi-Ning Chen; Xing-Dong Zhao; Jie Deng; Qin-Geng Li

doi:10.1107/S1600536812014328

. 2012 Apr 13;68(Pt 5):o1375. doi: 10.1107/S1600536812014328

tert-Butyl 6-amino-5-cyano-2-(2-methoxyethyl)nicotinate

Yi-Ning Chen ^a, Xing-Dong Zhao ^b, Jie Deng ^c, Qin-Geng Li ^a,^*

PMCID: PMC3381644 PMID: 22737103

Abstract

The title compound, C₁₄H₁₉N₃O₃, was synthesized by the reaction of 3-methoxypropionitrile, tert-butyl bromoacetate and ethoxymethylenemalononitrile. In the crystal, N—H⋯O hydrogen bonds link the molecules into chains propagating along the b axis.

Related literature

For a related structure, see: Wang et al. (2007 ▶). For applications of pyridines, see: Spurr (1995 ▶). For background to the synthesis of highly substituted pyridines, see: Chun et al. (2009 ▶, 2011 ▶).

Experimental

Crystal data

C₁₄H₁₉N₃O₃
M _r = 277.32
Monoclinic,
a = 10.1155 (4) Å
b = 15.2482 (5) Å
c = 19.4882 (6) Å
β = 99.853 (3)°
V = 2961.59 (18) Å³
Z = 8
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 130 K
0.35 × 0.30 × 0.30 mm

Data collection

Agilent Xcalibur Eos diffractometer
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2010 ▶) T _min = 0.902, T _max = 1.000
5419 measured reflections
2608 independent reflections
2094 reflections with I > 2σ(I)
R _int = 0.020

Refinement

R[F ² > 2σ(F ²)] = 0.040
wR(F ²) = 0.100
S = 1.05
2608 reflections
191 parameters
4 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.16 e Å⁻³
Δρ_min = −0.22 e Å⁻³

Data collection: CrysAlis PRO (Agilent, 2010 ▶); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: OLEX2 (Dolomanov et al., 2009 ▶); software used to prepare material for publication: OLEX2.

Supplementary Material

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536812014328/cv5269sup1.cif

e-68-o1375-sup1.cif^{(18.4KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812014328/cv5269Isup2.hkl

e-68-o1375-Isup2.hkl^{(128.2KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536812014328/cv5269Isup3.cml

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
N2—H2A⋯O3ⁱ	0.88 (1)	2.25 (1)	3.0186 (18)	146 (2)
N2—H2B⋯O1ⁱ	0.88 (1)	2.00 (1)	2.8427 (18)	159 (2)

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Symmetry code: (i) Inline graphic .

Acknowledgments

The authors thank Yin Ping, Fang Bo and Fochon Pharma, Inc.

supplementary crystallographic information

Comment

Pyridines can be found in many natural products and biologically active compounds (Spurr, 1995). Thus, the synthesis of highly substituted pyridines has attracted much attention (Chun et al. 2009, 2011). We synthesized the title compound (I). Herein we present its crystal structure.

In (I) (Fig. 1), all bond lengths and angles are normal and comparable with those observed in the related compound methyl 6-amino-5-cyano-4-(4-fluorophenyl)-2-methylpyridine-3-carboxylate (Wang et al., 2007).

In the crystal structure of (I), intermolecular N—H···O hydrogen bonds (Table 1) link the molecules into chains propagated along the b axis.

Experimental

A mixture of zinc powder (0.65 g) and 3-methoxypropionitrile (0.85 g) in tetrahydrofuran (10 ml) was refluxed, then tert-Butyl bromoacetate (1.95 g) was added dropwise. Keep stirring under reflux for 1 h. Ethoxymethylenemalononitrile (1.22 g) was added, the reaction mixture was stirred under reflux for 2 h to afford the title compound (I) (Chun et al. 2009, 2011). Single crystals were grown by slow evaporation of a solution of Pet: EtOAc=5:1 at room temperature.