2,5-Bis(4-methyl­phen­yl)-4-oxopenta­noic acid

Jun Wang; Xiaomei Zhuang; Yong Hou

doi:10.1107/S1600536810037323

. 2010 Sep 25;66(Pt 10):o2621. doi: 10.1107/S1600536810037323

2,5-Bis(4-methylphenyl)-4-oxopentanoic acid

Jun Wang ^a, Xiaomei Zhuang ^a,^*, Yong Hou ^a

PMCID: PMC2983153 PMID: 21587595

Abstract

The title compound, C₁₉H₂₀O₃, was obtained from 1,4-bis(4-methylphenyl)but-3-yn-2-one in the presence of carbon monoxide by Ni(CN)₂ catalysis in a basic aqueous medium. Intermolecular O—H⋯O hydrogen bonds lead to the formation of hydrogen-bonded carboxylic acid dimers [graph-set motif R ² ₂(8)]. Weak C—H⋯O hydrogen bonds between neighbouring dimers further extend the structure to give rise to a three-dimensional supramolecular network.

Related literature

For general background to transition metal-mediated carbonylation reactions, see: Collins (1999 ▶); Arzoumanian et al. (1995 ▶). For a similar structure, see: Garcia-Gutierrez et al. (2004 ▶). For bond length values, see: Allen et al. (1987 ▶). For hydrogen-bonding motifs, see: Bernstein et al. (1995 ▶).

Experimental

Crystal data

C₁₉H₂₀O₃
M _r = 296.35
Monoclinic,
a = 11.846 (2) Å
b = 13.155 (3) Å
c = 11.755 (2) Å
β = 115.98 (3)°
V = 1646.7 (7) Å³
Z = 4
Mo Kα radiation
μ = 0.08 mm⁻¹
T = 293 K
0.25 × 0.22 × 0.19 mm

Data collection

Bruker APEXII area-detector diffractometer
12947 measured reflections
2956 independent reflections
1474 reflections with I > 2σ(I)
R _int = 0.062

Refinement

R[F ² > 2σ(F ²)] = 0.050
wR(F ²) = 0.173
S = 1.01
2956 reflections
202 parameters
H-atom parameters constrained
Δρ_max = 0.24 e Å⁻³
Δρ_min = −0.18 e Å⁻³

Data collection: APEX2 (Bruker, 2004 ▶); cell refinement: APEX2 and SAINT (Bruker, 2004 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: XP in SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXL97.

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810037323/zl2309sup1.cif

e-66-o2621-sup1.cif^{(16.8KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810037323/zl2309Isup2.hkl

e-66-o2621-Isup2.hkl^{(145.1KB, 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
C17—H17⋯O1ⁱ	0.93	2.50	3.418 (4)	169
C15—H15⋯O2ⁱⁱ	0.93	2.56	3.452 (4)	160
O2—H2A⋯O3ⁱⁱⁱ	0.82	1.83	2.638 (2)	169

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

Acknowledgments

The work was supported by Zhongshan Polytechnic.

supplementary crystallographic information

Comment

Transition-metal-mediated carbonylation reactions are of great research interest in recent years (Collins, 1999). Amongst the many metal-mediated syntheses used, catalysis by nickel cyanide in aqueous media under phase transfer conditions has attracted particular attention (Arzoumanian et al., 1995) and numerous lactones and their hydrolysis products have been synthesized using this system. Herein, we chose 1,4-di(4-methylbenzyl)but-3-yn-2-one as a carbonylation substrate to be reacted in the presence of Ni(CN)₂ and carbon monoxide in a biphasic toluene/basic aqueous medium to give the title compound.

The structure of the title compound is depicted in Fig. 1. The C—C bond lengths show normal values (Allen et al., 1987), and the C—O and C═O bond lengths are comparable to those observed in simliar structures (Garcia-Gutierrez et al., 2004). The molecules form dimers with neighboring molecules through O—H···O hydrogen bonding with an R²₂(8) graph set motif (Bernstein et al., 1995). These dimers are further linked by C—H···O hydrogen bonds (Table 1) to form a three-dimensional supramolecular network (Fig. 2).

Experimental

A typical experiment was performed as follows: in a round-bottomed flask toluene (25 ml) and 1 M aqueous NaOH (10 ml) were degassed and saturated with CO under atmospheric pressure before Ni(CN)₂.4H₂O (1.0 mmol) and tetrabutylammonium bromide (0.3 mmol) were introduced, and the mixture was kept at room temperature overnight with stirring while CO was slowly (2–3 min) bubbled through the solution. To the yellow two-phase mixture was then added 10 mmol of 1,4-di(4-methylbenzyl)but-3-yn-2-one, and stirring and flow of CO at a flow rate of 3 ml min^-1 were maintained for 5 h at 393 K. At the end of the reaction, ethyl ether (2 × 20 ml) was used to eliminate the impurities. The aqueous phase was acidified with diluted HCl at pH = 1. Ethyl ether (2 × 20 ml) was used to extract the product. The organic phase was dried over Na₂SO₄ and evaporated to obtain a yellow powder. During recrystallization, the yellow block crystals were obtained by slow evaporation of the solvent with a yield of 68%. m.p. 476–478 K; IR (KBr) cm^-1: 3052, 2980, 2948, 1716, 1705, 1669, 1607, 1573, 1465, 1416, 1379, 1345, 1285, 1246, 1232, 1217, 1186, 1150, 1068, 1044, 995, 972, 850.