(1-Bromo­naphthalen-2-yl)acetonitrile

Andria D Harris; Amy D Baucom; Jessica L Brown; Daniel S Jones; Craig A Ogle

doi:10.1107/S1600536808017418

. 2008 Jun 19;64(Pt 7):o1284. doi: 10.1107/S1600536808017418

(1-Bromonaphthalen-2-yl)acetonitrile

Andria D Harris ^a, Amy D Baucom ^a, Jessica L Brown ^a, Daniel S Jones ^a,^*, Craig A Ogle ^a,^*

PMCID: PMC2961673 PMID: 21202915

Abstract

The title compound, C₁₂H₈BrN, was prepared as a starting material for a Suzuki cross-coupling reaction with a pinacol ester. The torsion angle about the ring–methylene C—C bond is 30.7 (3)°, such that the N atom is displaced by 1.174 (4) Å from the plane of the naphthalene ring system.

Related literature

A search of the Cambridge Structural Database [Version 5.29 (Allen, 2002 ▶); CONQUEST (Bruno et al., 2002 ▶)] yielded one comparable structure, (4-bromonaphthalen-2-yl)acetonitrile (Refcode BAGTEJ; Duthie et al., 2001 ▶). graphic file with name e-64-o1284-scheme1.jpg

Experimental

Crystal data

C₁₂H₈BrN
M _r = 246.1
Monoclinic,
a = 11.3599 (13) Å
b = 7.2379 (8) Å
c = 11.8901 (15) Å
β = 102.538 (10)°
V = 954.31 (19) Å³
Z = 4
Cu Kα radiation
μ = 5.47 mm⁻¹
T = 295 (2) K
0.5 × 0.2 × 0.2 mm

Data collection

Enraf–Nonius CAD-4 diffractometer
Absorption correction: none
6502 measured reflections
1729 independent reflections
1558 reflections with I > 2σ(I)
R _int = 0.031
3 standard reflections every 75 reflections intensity decay: 2%

Refinement

R[F ² > 2σ(F ²)] = 0.025
wR(F ²) = 0.063
S = 1.01
1729 reflections
127 parameters
H-atom parameters constrained
Δρ_max = 0.35 e Å⁻³
Δρ_min = −0.51 e Å⁻³

Data collection: CAD-4 EXPRESS (Enraf–Nonius, 1994 ▶); cell refinement: CAD-4 EXPRESS; data reduction: XCAD4 (Harms & Wocadlo, 1995 ▶); program(s) used to solve structure: DIRDIF (Beurskens et al., 1999 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶).

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808017418/fl2183sup1.cif

e-64-o1284-sup1.cif^{(12.9KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808017418/fl2183Isup2.hkl

e-64-o1284-Isup2.hkl^{(83.5KB, hkl)}

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Acknowledgments

This work was supported in part by funds provided by the University of North Carolina at Charlotte.

supplementary crystallographic information

Comment

The title compound (Fig.1) was prepared as a starting material for a Suzuki cross coupling reaction with a pinacol ester. The C11—C12—N angle is 178.4 (3)°, and the plane of that grouping makes an angle of 42.5 (1)° with the plane of the naphthalene ring, while the N atom is displaced 1.174 (4) Å from the plane of the naphthalene ring. As shown in Figs. 2 and 3, the molecules form alternating layers when viewed edge-on and form columns when viewed along the b axis.

A search of the Cambridge Structural Database [Version 5.29; (Allen, 2002); CONQUEST, Version 1.10 (Bruno et al., 2002)] yielded one comparable structure, (4-bromonapthalen-2-yl)acetonitrile (Refcode BAGTEJ; Duthie et al., 2001). In that structure the acetonitrile C—C—N angle was 179.3°, and the plane of that grouping made an angle of 23.1° with the plane of the naphthalene ring. The N atom was displaced 0.287 Å from the plane of the naphthalene ring.

Experimental

Synthesis of 1-bromo-2-methylnaphthalene (II) (Fig. 4). A solution of 2-methylnaphthalene (I) in acetic acid was stirred while an equivalent amount of Br₂ in acetic acid was added dropwise at a rate that allowed the bromine color to dissipate between drops. Upon completion of addition the mixture was allowed to stir for 1 h at which time the entire mixture was poured into water. The organic phase was separated and washed repeatedly with water to remove the acetic acid. The product was dried with K₂CO₃ and used in the next step without further purification.

Synthesis of 1-bromo-2-(bromomethyl)naphthalene (III). N-Bromosuccinimide (1 eq) and benzoylperoxide (0.01 eq) were added to a solution of (II) dissolved in CCl₄. The reaction was then heated to reflux and the reaction progress was monitored with GC/MS. The reaction seemed to stall out at 3 h, and an additional portion of benzoylperoxide (0.01 eq) was added and allowed to reflux for an additional 3 h. The succinimide byproduct was removed by filtration from the cooled mixture. The CCl₄ was removed and the product (III) was recrystallized from isooctane.

Synthesis of the title compound (IV). KCN (1.1 eq) was dissolved in DMSO with stirring. III (1.0 eq) was added along with additional DMSO to the stirred reaction mixture. A slight exotherm was observed, and the homogeneous mixture was allowed to stir overnight. The reaction was judged to be complete by GC/MS analysis. The reaction mixture was poured into water with stirring. The product precipitated upon addition to water. After filtering, the product was dried on a watch glass, and crystals for the diffraction study were obtained by recrystallization from a 2:1 mixture of 1,2-dimethoxyethane and ethanol.