2-Phenyl-3-(trimethyl­sil­yl)propan-1-aminium chloride

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

doi:10.1107/S1600536811035410

. 2011 Sep 3;67(Pt 10):o2553. doi: 10.1107/S1600536811035410

2-Phenyl-3-(trimethylsilyl)propan-1-aminium chloride

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

PMCID: PMC3201342 PMID: 22058730

Abstract

The title compound, C₁₂H₂₂NSi⁺·Cl⁻, contains two formula units in the asymmetric unit and is a hydrochloride salt in which the amine N atom is protonated and the NH₃ ⁺ group forms hydrogen bonds with the Cl⁻ anion, forming a ribbon in the c-axis direction.

Related literature

For silicon-substituted β-phenylethyl amine and its 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 uses and applications of 3-amino-propylsilanes in nano technology and self-assembled monolayers, see: Li et al. (2009 ▶) and in reverse ionic liquids in oil extraction, see: Blasucci et al. (2010 ▶). For a description of the Cambridge Structural Database, see: Allen (2002 ▶).

Experimental

Crystal data

C₁₂H₂₂NSi⁺·Cl⁻
M _r = 243.85
Monoclinic,
a = 12.3716 (4) Å
b = 32.6920 (8) Å
c = 7.44256 (18) Å
β = 93.006 (2)°
V = 3006.01 (14) Å³
Z = 8
Cu Kα radiation
μ = 2.79 mm⁻¹
T = 295 K
0.47 × 0.10 × 0.06 mm

Data collection

Oxford Diffraction Xcalibur Ruby Gemini diffractometer
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009 ▶) T _min = 0.370, T _max = 1.000
11195 measured reflections
5882 independent reflections
3078 reflections with I > 2σ(I)
R _int = 0.049

Refinement

R[F ² > 2σ(F ²)] = 0.076
wR(F ²) = 0.276
S = 1.14
5882 reflections
279 parameters
H-atom parameters constrained
Δρ_max = 0.72 e Å⁻³
Δρ_min = −0.49 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/S1600536811035410/hg5087sup1.cif

e-67-o2553-sup1.cif^{(24.3KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811035410/hg5087Isup2.hkl

e-67-o2553-Isup2.hkl^{(288KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536811035410/hg5087Isup3.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
N1A—H1AA⋯Cl2ⁱ	0.89	2.23	3.114 (5)	173
N1A—H1AB⋯Cl1	0.89	2.25	3.136 (4)	172
N1A—H1AC⋯Cl1ⁱⁱ	0.89	2.36	3.168 (5)	152
N1B—H1BA⋯Cl2ⁱⁱ	0.89	2.30	3.166 (4)	163
N1B—H1BB⋯Cl2	0.89	2.28	3.165 (4)	171
N1B—H1BC⋯Cl1	0.89	2.35	3.222 (5)	165

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

Acknowledgments

RJB wishes to acknowledge the NSF–MRI program (grant CHE-0619278) for funds to purchase the diffractometer. YMH acknowledges partial support from NSF-Rise award # 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 insecticide and applications in pharmaceuticals (Frankel et al. 1968). Viewing these compounds as substituted 3-silylpropylamine 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).

In view of the importance of these compounds the structure of 2-phenyl-3-(trimethylsilyl)-propan-l-aminium chloride, C₁₂H₂₂ClNSi is reported. The title compound contains two formula units in the asymmetric unit and is a hydrochloride salt where the amine N is protonated and the NH₃⁺ group forms hydrogen bonds with the Cl^- anion. These hydrogen bonds form a ribbon in the c direction. The metrical parameters for the salt are in the normal range (Allen, 2002).

Experimental

To 5.20 g (44.4 mmol) benzylnitrile in 40 ml of dry THF under nitrogen atmosphere, cooled in an ice bath was added 28.0 ml of n-Bu Li (1.6 M) (44.8 mmol) dropwise. After the addition was complete the solution turned to a creamy slurry. The mixture was stirred for 10 minutes then the ice bath was removed and 5.54 g of chloromethyltrimethyl silane (6.3 ml) was added dropwise. After the addition was complete the mixture was stirred for 2 h at room temperature. The reaction was worked up by water addition and extraction with ether twice (25 ml). The organic layers were combined and washed with saturated NaCl solution, dried (MgSO4). The solvent was removed to give 3-trimethylsilyl-2-phenyl-propionitrile, as yellowish liquid 7.5 g (78%). 2.0 g of 3-trimethylsilyl-2-phenyl-propionitrile were dissolved in 5 ml of dry THF and heated to 343 K in a distillation set up. 3.0 ml of BH₃.DMS (10 M) was added dropwise over a period of 10 minutes. Dimethylsulfide (DMS) distilled off the reaction mixture and was collected in the receiver. The mixture was heated for 15 minutes then cooled to room temperature. A reflux condenser was connected to the reaction flask and 10 ml of 6 M HCl was added carefully and slowly. After the addition was complete and no more gas evolved the mixture was heated for 30 minutes at reflux. The reaction mixture was cooled to room temperature, transferred to a beaker. KOH pellets were added slowly to the solution to neutralize the acid. The mixture was extracted with 2x25 ml of ether. The organic layers were combined and 5 ml of concentrated HCl was added. The aqueous layer was allowed to evaporate to give white solid. The solid was washed with ether and filtered to give 0.98 g (41%) of the title compound. A sample was dissolved in water and allowed to evaporate slowly to give clear crystals of the title compound used for x-ray crystallography.

¹H NMR (DMSO-d₆, 400 MHz): δ (p.p.m.) = 7.85 (br, 3H), 7.31 (m, 5H), 2.94 (m,3H), 1.00 (dd,1H, J= 14.5, 3.5 Hz), 0.92 (dd, 1 H, J = 14.5, 11 Hz), -0.28 (s, 9H). ¹³C NMR (DMSO-d₆,, 100 MHz): δ (p.p.m.) 142.24, 128.65, 127.91, 127.16, 46.89, 39.78, 21.01, -1.21. Exact Mass = 207.084401 (M⁺ - HCl) Mass Spec (EI) direct probe M/z: 208 (M—Cl), 192 (M+ –NH₂Cl), 177 (M—CH₂NH₃Cl), 147, 121, 104, 91, 73 (base).