Crystal structure of (Z)-1-phenyl-3-styryl­undeca-2-en-4,10-diyn-1-ol

Rakesh Ganguly; Sally; Philip Wai Hong Chan

doi:10.1107/S205698901402742X

. 2015 Jan 1;71(Pt 1):o64. doi: 10.1107/S205698901402742X

Crystal structure of (Z)-1-phenyl-3-styrylundeca-2-en-4,10-diyn-1-ol

Rakesh Ganguly ^a,^*, Sally ^b, Philip Wai Hong Chan ^b

PMCID: PMC4331854 PMID: 25705512

Abstract

The molecule of the title compound, C₂₅H₂₄O, obtained by acid-catalysed 1,3-migration of an alcohol group, is T-shaped. The planes of the two phenyl rings are inclined to one another by 81.9 (2)°. In the crystal, molecules are linked by O—H⋯O hydrogen bonds, forming chains along [001].

Keywords: crystal structure; 1,3-migration; alcohol group; catalytic cyclization; styrylundecanene.

Related literature

For the 1,3-migration of an alcoholic group adjacent to a vinyl group in the presence of a Lewis acid, see: Piotti & Alper (1997 ▸); Poloukhtine & Popik (2005 ▸). For catalytic cyclization of alcohols containing a number of unsaturated groups, see: Teo et al. (2014 ▸). graphic file with name e-71-00o64-scheme1.jpg

Experimental

Crystal data

C₂₅H₂₄O
M _r = 340.44
Trigonal,
a = 17.867 (2) Å
c = 5.3290 (6) Å
V = 1473.3 (4) Å³
Z = 3
Mo Kα radiation
μ = 0.07 mm⁻¹
T = 103 K
0.34 × 0.04 × 0.04 mm

Data collection

Bruker Kappa APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2013 ▸) T _min = 0.74, T _max = 1.00
14182 measured reflections
4846 independent reflections
2945 reflections with I > 2σ(I)
R _int = 0.078

Refinement

R[F ² > 2σ(F ²)] = 0.058
wR(F ²) = 0.129
S = 0.98
4846 reflections
235 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 0.39 e Å⁻³
Δρ_min = −0.24 e Å⁻³

Data collection: APEX2 (Bruker, 2013 ▸); cell refinement: SAINT (Bruker, 2013 ▸); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick 2008 ▸); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2008 ▸); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012 ▸) and Mercury (Macrae et al., 2008 ▸); software used to prepare material for publication: SHELXL2014, PLATON (Spek, 2009 ▸) and publCIF (Westrip, 2010 ▸).

Supplementary Material

Crystal structure: contains datablock(s) I, New_Global_Publ_Block. DOI: 10.1107/S205698901402742X/su5038sup1.cif

e-71-00o64-sup1.cif^{(427.6KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S205698901402742X/su5038Isup2.hkl

e-71-00o64-Isup2.hkl^{(265.7KB, hkl)}

Click here for additional data file.^{(7.1KB, cml)}

Supporting information file. DOI: 10.1107/S205698901402742X/su5038Isup3.cml

Click here for additional data file.^{(1.4MB, tif)}

. DOI: 10.1107/S205698901402742X/su5038fig1.tif

A view of the molecular structure of the title compound, with atom labelling. Displacement ellipsoids are drawn at the 50% probability level.

Click here for additional data file.^{(1.8MB, tif)}

c . DOI: 10.1107/S205698901402742X/su5038fig2.tif

A partial view along the c axis of the crystal packing of the title compound. Hydrogen bonds are shown as dashed lines (see Table 1 for details).

Click here for additional data file.^{(16.4KB, tif)}

. DOI: 10.1107/S205698901402742X/su5038fig3.tif

Reaction scheme.

CCDC reference: 1009363

Additional supporting information: crystallographic information; 3D view; checkCIF report

Table 1. Hydrogen-bond geometry (, ).

DHA	DH	HA	D A	DHA
O1H1AO1ⁱ	0.84	1.83	2.652(3)	166

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Symmetry code: (i) Inline graphic .

supplementary crystallographic information

S1. Comment

1,3-migration of an alcoholic group adjacent to a vinyl group in the presence of a Lewis-acid is widely known (Piotti & Alper, 1997). One such example was demonstrated recently in the preparation of 4-(α-hydroxybenzyl)-1-tert-butyldimethylsilyloxy-4-cyclodecene-2,6-diyne (Poloukhtine & Popik, 2005). In addition, alcohols containing many unsaturated groups provide an access to a myriad of types of functionalization such as catalytic cyclization (Teo et al., 2014). Herein, we report on the synthesis and crystal structure of the title compound, obtained by the acid-catalyzed 1,3-migration of an alcoholic group.

The molecular structure of the title compound is illustrated in Fig. 1. The molecule is T-shaped with the two phenyl ring inclined to one another by 81.9 (2) °.

In the crystal, molecules are linked by O—H···O hydrogen bonds forming chains along the c axis direction (Table 1 and Fig. 2).

S2. Synthesis and crystallization

The synthesis of the title compound is illustrated in Fig. 3. (Z)-1-phenyl-3-styrylundeca-1-en-4,10-diyn-3-ol (1mmol, 340.5 mg) was dissolved in 10 ml of CH₂Cl₂. DMAP [4-(dimethylamino)pyridine; 0.1 mmol, 12 mg], triethylamine (5 mmol, 0.70 ml) and acetic anhydride (5 mmol, 0.47 ml) were added sequentially and the reaction mixture was stirred overnight. It was then washed with saturated sodium bicarbonate and extracted twice with CH₂Cl₂. The organic layers were combined, dried with MgSO₄ and the solvent was removed under reduced pressure. The resulting oil was purified by column chromatography with hexane/ethylacetate as eluent. The product was recrystallized with ethylacetate to give a colourless compound in 80% yield. Slow evaporation of a solution in ethylacetate gave needle-like crystals. ¹H NMR (400 MHz, CDCl₃) 1.71–1.83 (m, 4H), 1.97 (t, 1H), 2.20 (s, 1H), 2.26–2.30 (m, 2H), 2.55 (t, 2), 5.90 (d, 1H), 6.09 (d, 1H), 6.68 (d, 1H), 6.99 (d, 1H), 7.21–7.47 (m, 10H) 13 C NMR (100 MHz, CDCl3) 18.0, 19.2, 27.7, 27.7, 68.8, 72.5, 75.3, 84.0, 97.9, 124.1, 125.9, 126.8, 127.7, 127.9, 128.6, 128.6, 132.4, 136.8, 140.4, 142.7

S3. Refinement

The OH and C-bound H atoms were included in calculated positions and treated as riding atoms: O—H = 0.84 Å, C—H = 0.95 - 1.00 Å with U_iso(H) = 1.5U_eq(O) for the OH H atom and = 1.2U_eq(C) for other H atoms.