Allyl 4-hydroxy­phenyl carbonate

Víctor Hugo Flores Ahuactzin; Delia López; Sylvain Bernès

doi:10.1107/S1600536809022387

. 2009 Jun 17;65(Pt 7):o1603. doi: 10.1107/S1600536809022387

Allyl 4-hydroxyphenyl carbonate

Víctor Hugo Flores Ahuactzin ^a, Delia López ^a, Sylvain Bernès ^b,^*

PMCID: PMC2969403 PMID: 21582877

Abstract

The title molecule, C₁₀H₁₀O₄, is a functionalized carbonate used in the synthetic route to organic glasses. The central CH fragment of the allyl group is disordered over two positions, with occupancies in a 0.758 (10):0.242 (10)ratio. This disorder reflects the torsional flexibility of the oxygen–allyl group, although both disordered parts present the expected anticlinal conformation, with O—CH₂—CH=CH₂ torsion angles of −111 (2) and 119.1 (4)°. The crystal structure is based on chains parallel to [010], formed by O⋯H—O hydrogen bonds involving hydroxyl and carbonyl groups as donors and acceptors, respectively. The molecular packing is further stabilized by two weak C—H⋯π contacts from the benzene ring of the asymmetric unit with two benzene rings of neighboring molecules.

Related literature

The crystal structures of two allyl carbonates have been reported to date, see: Michelet et al. (2003 ▶); Burns & Forsyth (2008 ▶). For the use of allyl ester and allyl carbonate derivatives as precursors for organic glasses, see: Herrera et al. (2003 ▶); Herrera (2006 ▶).

Experimental

Crystal data

C₁₀H₁₀O₄
M _r = 194.18
Monoclinic,
a = 5.8148 (7) Å
b = 7.5413 (11) Å
c = 11.4499 (17) Å
β = 93.515 (10)°
V = 501.15 (12) Å³
Z = 2
Mo Kα radiation
μ = 0.10 mm⁻¹
T = 298 K
0.60 × 0.30 × 0.24 mm

Data collection

Bruker P4 diffractometer
Absorption correction: none
2559 measured reflections
1233 independent reflections
1042 reflections with I > 2σ(I)
R _int = 0.025
3 standard reflections every 97 reflections intensity decay: 0.5%

Refinement

R[F ² > 2σ(F ²)] = 0.037
wR(F ²) = 0.109
S = 1.06
1233 reflections
137 parameters
2 restraints
H-atom parameters constrained
Δρ_max = 0.10 e Å⁻³
Δρ_min = −0.17 e Å⁻³

Data collection: XSCANS (Siemens, 1996 ▶); cell refinement: XSCANS; data reduction: XSCANS; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: Mercury (Macrae et al., 2006 ▶); software used to prepare material for publication: SHELXL97.

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809022387/bq2136sup1.cif

e-65-o1603-sup1.cif^{(15.8KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809022387/bq2136Isup2.hkl

e-65-o1603-Isup2.hkl^{(60.9KB, 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
O14—H14⋯O6ⁱ	0.88	1.91	2.762 (2)	160
C10—H10A⋯Cgⁱ	0.93	2.90	3.612 (2)	135
C13—H13A⋯Cgⁱⁱ	0.93	2.81	3.513 (3)	133

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Symmetry codes: (i) Inline graphic ; (ii) . Cg is the centroid of the benzene ring.

Acknowledgments

Financial support from VIEP-BUAP (grant 7-/I/NAT/05–06) is acknowledged. VHFA also express his sincere thanks to VIEP for a partial scholarship.

supplementary crystallographic information

Comment

We have synthesized some functionalized aromatic allyl ester (Herrera et al., 2003) and allyl carbonate compounds (Herrera, 2006) as intermediates in the preparation of new diallylcarbonate monomers, which are potential precursors of organic glasses. One representative example is the title molecule, which includes phenol and allyl functional groups as substitutents of the carbonate core (Fig. 1).

The allyl group presents a degree of flexibility, resulting in two disordered positions for the methylene group, C21 and C22, with site occupation factors 0.758 (10) and 0.242 (10), respectively (Fig. 1, inset). Regardless of the position for the CH₂ fragment, O—allyl chain displays the expected anticlinal conformation, characterized by torsion angles O—CH₂—CH═CH₂ of -111 (2)° and 119.1 (4)°. A similar disorder was previously observed for a closely related phenol allylic derivative, allyl-4-hydroxybenzoate (Herrera et al., 2003). To date, only two acyclic allyl carbonate systems have been X ray characterized, both with non disordered allyl groups. The anticlinal conformation has been stabilized in the first molecule, with O—allyl torsion angle of -131.4° (Michelet et al., 2003), while in the most recent report, a synperiplanar O—allyl group is observed, the torsion angle being 9.7° (Burns & Forsyth, 2008). This very limited set of structurally characterized allyl carbonate derivatives does not allow to determine the factors influencing the stable conformation for these molecules in the solid state. In contrast, a number of allyl ester derivatives have been X-ray characterized, with conformations restricted to two attractors (Herrera et al., 2003).

The crystal structure of the title compound is based on chains running along [010], formed through O···H—O bonds, where carbonyl functionalities act as acceptor and hydroxyl functionalities as donor groups. Moreover, two aryl C—H groups of the benzene ring of the asymmetric unit form stabilizing C—H···π contacts with the centroids of two symmetry-related benzene rings (Fig. 2).

Experimental

Allyl 4-hydroxyphenyl-carbonate was synthesized by reacting hydroquinone and allylchloroformate in the presence of NaOH at 273 K for 2 h., affording a white powder (Yield: 43%). After recrystallization from a mixture of methylene chloride and hexane (7:3), colourless crystals were obtained. Anal. calcd for C₁₀H₁₀O₄: C 61.85, H 5.19; found: C 61.85, H 5.25.