2,2-Dimethyl-5-(2-naphthyl­amino­methyl­ene)-1,3-dioxane-4,6-dione

Rui Li; Zhen-Yu Ding

doi:10.1107/S1600536809038458

. 2009 Sep 30;65(Pt 10):o2576. doi: 10.1107/S1600536809038458

2,2-Dimethyl-5-(2-naphthylaminomethylene)-1,3-dioxane-4,6-dione

Rui Li ^a,^*, Zhen-Yu Ding ^a

PMCID: PMC2970245 PMID: 21578013

Abstract

There are two unique molecules in the asymmetric unit of the title compound, C₁₇H₁₅NO₄, which are linked into chains via intermolecular N—H⋯O and C—H⋯O interactions; the chains are linked via weak C—H⋯O interactions, forming a parallel sheet structure. The molecule is approximately planar, with dihedral angles of 19.91 (4) and 11.06 (4)° between the naphthyl ring and the aminomethylene group, and between the aminomethylene unit and the planar part of the dioxane ring, respectively. The dioxane ring adopts a half-boat conformation, with the C atom between the dioxane O atoms 0.595 (8) Å out of the plane through the remaining atoms. The molecule has an intramolecular N—H⋯O hydrogen bond which stabilizes the planar conformation.

Related literature

For the synthesis of related compounds, see: Cassis et al. (1985 ▶). For the synthesis of related antitumor precursors, see: Ruchelman et al. (2003 ▶). For the crystal structures of other 5-arylaminomethylene-2,2-dimethyl-1,3-dioxane-4,6-dione derivatives, see: Li et al. (2009a ▶,b ▶,c ▶).

Experimental

Crystal data

C₁₇H₁₅NO₄
M _r = 297.30
Triclinic,
a = 10.6204 (17) Å
b = 11.8220 (19) Å
c = 12.0143 (19) Å
α = 78.237 (2)°
β = 86.786 (2)°
γ = 82.469 (2)°
V = 1463.4 (4) Å³
Z = 4
Mo Kα radiation
μ = 0.10 mm⁻¹
T = 153 K
0.25 × 0.22 × 0.20 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: none
9205 measured reflections
6490 independent reflections
4313 reflections with I > 2σ(I)
R _int = 0.024

Refinement

R[F ² > 2σ(F ²)] = 0.048
wR(F ²) = 0.127
S = 1.11
6490 reflections
410 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.23 e Å⁻³
Δρ_min = −0.19 e Å⁻³

Data collection: SMART (Bruker, 2001 ▶); cell refinement: SAINT (Bruker, 2001 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2009 ▶).

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809038458/bv2127sup1.cif

e-65-o2576-sup1.cif^{(27.3KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809038458/bv2127Isup2.hkl

e-65-o2576-Isup2.hkl^{(317.6KB, 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
N1—H1⋯O3	0.92 (2)	2.11 (2)	2.7681 (18)	127.2 (16)
N1—H1⋯O7	0.92 (2)	2.35 (2)	3.184 (2)	150.9 (17)
N2—H2⋯O7	0.91 (2)	2.15 (2)	2.7858 (18)	126.7 (17)
N2—H2⋯O3	0.91 (2)	2.36 (2)	3.1893 (19)	152.9 (17)
C7—H7⋯O4	0.95	2.50	2.833 (2)	101
C14—H14⋯O4ⁱ	0.95	2.51	3.354 (2)	148
C24—H24⋯O8	0.95	2.45	2.804 (2)	102
C26—H26⋯O3	0.95	2.46	3.2569 (19)	142

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Symmetry code: (i) Inline graphic .

Acknowledgments

This work was supported by the National Natural Science Foundation of China (30901743)

supplementary crystallographic information

Comment

5-Arylaminomethylene-2,2-dimethyl-1,3-dioxane-4,6-diones are key intermediates and can be used to synthesize 4(1H)quinolone derivatives by thermolysis (Cassis et al., 1985) which can be used as precursors for anticancer agents, anti-malarial agents and reversible (H+/K+) ATPase inhibitors (Ruchelman et al.,2003). The molecule (Fig. 1) is approximately planar with dihedral angles of 19.91 (4)° and 11.06 (4)° between the benzyl ring and the aminomethylene group, and between the aminomethylene unit and the planar part of the dioxane ring, respectively. In addition, the dioxane ring of the title compound adopts a half-boat conformation, in which the C atom between the dioxane oxygen atoms is -0.595 (8) Å out-of-plane. The intramolecular N—H···O hydrogen bond (Table 1) is stabilizing the planar conformation in the molecule.

Experimental

An ethanol solution of 2,2-dimethyl-1,3-dioxane-4,6-dione (1.44 g, 0.01 mol) with methylorthoformate (1.27 g, 0.012 mol) was heated to reflux for 2 h, then the arylamine (1.32 g, 0.01 mol) was added into the solution. The mixture was heated under reflux for another 10 h and then filtered. Single crystals were obtained from the filtrate after 2 days.