2-(4-Hy­droxy­phen­yl)-3-(trimethyl­sil­yl)propanaminium chloride

Yousef M Hijji; Ray J Butcher; Jerry P Jasinski; Zachary White; Robert C Rosenberg

doi:10.1107/S1600536811037639

. 2011 Sep 30;67(Pt 10):o2694. doi: 10.1107/S1600536811037639

2-(4-Hydroxyphenyl)-3-(trimethylsilyl)propanaminium chloride

Yousef M Hijji ^a, Ray J Butcher ^b,^*, Jerry P Jasinski ^c, Zachary White ^b, Robert C Rosenberg ^b

PMCID: PMC3201541 PMID: 22058791

Abstract

In the title crystal structure, C₁₂H₂₂NOSi⁺·Cl⁻, anions and cations are linked via O—H⋯Cl, N—H⋯Cl and N—H⋯O hydrogen bonds to form a two-dimensional network parallel to (101). Within the hydrogen-bonded network, R ₄ ²(22) ring motifs are stacked along [010].

Related literature

For silicon-substituted β-phenylethyl amines and their biological activity, see: Frankel et al. (1968 ▶). For applications of β-phenylethyl amine in alkaloid synthesis via the Pictet–Spengler reaction, see: Lorenz et al. (2010 ▶). For the uses and applications of 3-amino-propylsilanes in nanotechnology and self-assembled monolayers, see: Li et al. (2009 ▶). For the uses and applications in reverse ionic liquids in oil extraction, see: Blasucci et al. (2010 ▶). For a related structure, see: Hijji et al. (2011 ▶). For standard bond lengths, see: Allen et al. (1987 ▶). For hydrogen-bond motifs, see: Bernstein et al. (1995 ▶).

Experimental

Crystal data

C₁₂H₂₂NOSi⁺·Cl⁻
M _r = 259.85
Monoclinic,
a = 14.2611 (4) Å
b = 6.7587 (2) Å
c = 16.0316 (9) Å
β = 91.252 (3)°
V = 1544.86 (11) Å³
Z = 4
Cu Kα radiation
μ = 2.79 mm⁻¹
T = 295 K
0.44 × 0.18 × 0.06 mm

Data collection

Oxford Diffraction Xcalibur Ruby Gemini diffractometer
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009 ▶) T _min = 0.713, T _max = 1.000
5741 measured reflections
3065 independent reflections
2023 reflections with I > 2σ(I)
R _int = 0.034

Refinement

R[F ² > 2σ(F ²)] = 0.061
wR(F ²) = 0.244
S = 1.14
3065 reflections
146 parameters
H-atom parameters constrained
Δρ_max = 0.42 e Å⁻³
Δρ_min = −0.46 e Å⁻³

Data collection: CrysAlis PRO (Oxford Diffraction, 2009 ▶); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXTL.

Supplementary Material

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536811037639/lh5328sup1.cif

e-67-o2694-sup1.cif^{(17.5KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811037639/lh5328Isup2.hkl

e-67-o2694-Isup2.hkl^{(150.4KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536811037639/lh5328Isup3.cml

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
O1—H1⋯Clⁱ	0.82	2.23	3.012 (4)	160
N1—H1A⋯Clⁱⁱ	0.89	2.39	3.146 (3)	143
N1—H1B⋯O1ⁱⁱⁱ	0.89	2.18	2.941 (5)	143
N1—H1C⋯Cl	0.89	2.21	3.093 (4)	172

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

Acknowledgments

RJB wishes to acknowledge the NSF–MRI program (grant No. CHE-0619278) for funds to purchase the diffractometer. YMH acknowledges partial support from the NSF Rise award (grant No. HRD 0627276).

supplementary crystallographic information

Comment

The title compound is a substituted α-phenyethylaminium chloride. Phenylethyl amines are substrates for dopamine-β-hydroxylase and are of biological importance. Silicon substituted phenylethyl amines have been investigated for biological activity and use as insecticides and have applications as pharmaceuticals (Frankel et al. 1968). These compounds can be viewed as substituted 3-silylpropylamines, where they have application in monolayer construction and nanotechnology (Li et al. 2009) and use in oil recovery via reverse ionic liquids (Blasucci et al., 2010). Phenylethyl amines are important building blocks in isoquinoline alkaloid synthesis via Pictet–Spengler (Lorenz et al. 2010). A related structure has been reported (Hijji et al., 2011).

In view of the importance of these compounds the structure of 4-(2-ammonium-1-trimethylsilanylmethyl-ethyl)-phenol chloride, is reported herein. The title compound is a hydrochloride salt and the Cl^- anion forms hydrogen bonds with both the NH₃⁺ and phenol groups forming R²₄(22) ring motifs (Bernstein et al., 1995) as shown in Fig. 2. In the crystal, anions and cations are linked via O—H···Cl, N—H···Cl and N—H···O hydrogen bonds to form a two-dimensional network parallel to (101) as is shown in Fig. 3. The bond lengths (Allen et al., 1987) and angles are in normal ranges.

Experimental

To a solution of 4-hydroxyphenylacetonitrile (3.0 g, 22.55 mole) dissolved in 20 ml dry THF, cooled in an ice bath, was added (14.5 ml, 23.2 mmol) n-BuLi (1.6 M, hexane) drop wise. After the addition was complete the mixture was stirred for 15 minutes then (4.5 g, 26.3 mmol) benzyl bromide was added slowly. 20 ml of THF and 15 ml of HMPA were added to the mixture while the flask was in the ice bath. The mixture was stirred for an additional 1 h in the ice bath and 4 h at RT. Aqueous work up gave a solid, m.p 335–336 K,(3.5 g 70% yield)) of 4-benzyloxyphenylacetonitrile. Alkylation of (2.0 g, 8.97 mmol) (III) by treatment with (6 ml, 9.6 mmol) of n-BuLi (1.6M, hexanes) then chloromethyltrimethylsilane (1.14 g, 9.33 mmol) for 2 h at RT and work up to give (1.35 g, 48.7% yield) of 2-(4-benzyloxy-phenyl)-3-trimethylsilyl-propionitrile m.p. 376–377 K. Reduction of (1.0 g, 3.23 mmol) of IV in 10 ml of dry THF with (0.5 ml, 5.0 mmol) of BH3.DMS (10 M in DMS) followed by acid hydrolysis with HCl and neutralization with NaOH pellets then product isolation and acidification (HCl) gave a white solid (0.81 g, 72% yield). m.p. 468–469 K of 1-(4-Benzyloxy-phenyl)-2-trimethylsilanyl-ethyl-ammonium chloride. Catalytic hydrogenation of (0.5 g, 1.43 mmol) of in 60 ml of ethanol and 0.2 g Pd/C (10%) gave a white solid (0.25 g, 67% yield) of the title compound. A sample was taken and dissolved in water then the solvent was allowed to evaporate slowly to provide clear crystals of the title compound used for X-ray measurements.

¹H NMR (DMSO-d₆, 400 MHz): δ (p.p.m.) = 9.35 (s, 1H),7.50 (br s, 3H) 7.05 (d, 2H, J = 8.48 Hz), 6.72 (d, 2H, J = 8.48 Hz), 2.84 (m, 3H), 0.92 (dd,1 H, J = 14.5, 3.5 Hz), 0.914 (dd, 1 H, J = 14.5, 11.0 Hz), -0.26 (s, 9H) Mass spec: 207 (M—NH₃Cl), 172, 165, 149, 134, 91, 73 ¹³C NMR (DMSO-d₆, 100 MHz): δ (p.p.m.) = 156.55, 132.53, 129.22, 115.97, 47.80, 39.39, 21.50, -.836.