trans-rac-[1-Oxo-2-phenethyl-3-(2-thien­yl)-1,2,3,4-tetra­hydro­isoquinolin-4-yl]methyl 4-methyl­benzene­sulfonate

Mehmet Akkurt; Sema Öztürk Yıldırım; Milen G Bogdanov; Meglena I Kandinska; Orhan Büyükgüngör

doi:10.1107/S1600536808029309

. 2008 Sep 17;64(Pt 10):o1955–o1956. doi: 10.1107/S1600536808029309

trans-rac-[1-Oxo-2-phenethyl-3-(2-thienyl)-1,2,3,4-tetrahydroisoquinolin-4-yl]methyl 4-methylbenzenesulfonate

Mehmet Akkurt ^a,^*, Sema Öztürk Yıldırım ^a, Milen G Bogdanov ^b, Meglena I Kandinska ^b, Orhan Büyükgüngör ^c

PMCID: PMC2959401 PMID: 21201159

Abstract

The title compound, C₂₉H₂₇NO₄S₂, was synthesized by reaction of trans-rac-4-(hydroxymethyl)-2-phenethyl-3-(thiophen-2-yl)-3,4-dihydroisoquinolin-1(2H)-one and 4-methylbenzene-1-sulfonyl chloride in the presence of Et₃N in CH₂Cl₂. The relative orientations of the benzene ring (A) of the 3,4-dihydroisoquinolinone ring system, the thiophene ring (B), the benzene ring (C) of the methylbenzene group and the phenyl ring (D) result in the following dihedral angles: A/B = 80.91 (16), A/C = 22.79 (18), A/D = 9.9 (2), B/C = 80.73 (19), B/D = 88.9 (2) and C/D = 29.9 (2)°. The crystal structure is stabilized by weak intermolecular C—H⋯O hydrogen bonds and C—H⋯π interactions.

Related literature

For chemical background, see: Kandinska et al. (2006 ▶); Rothweiler et al. (2008 ▶). For ring puckering parameters, see: Cremer & Pople (1975 ▶).

Experimental

Crystal data

C₂₉H₂₇NO₄S₂
M _r = 517.66
Triclinic,
a = 7.2529 (3) Å
b = 8.6727 (4) Å
c = 20.9899 (10) Å
α = 86.021 (4)°
β = 87.396 (4)°
γ = 78.330 (4)°
V = 1289.24 (10) Å³
Z = 2
Mo Kα radiation
μ = 0.24 mm⁻¹
T = 293 K
0.58 × 0.52 × 0.48 mm

Data collection

STOE IPDS 2 diffractometer
Absorption correction: integration (X-RED32; Stoe & Cie, 2002 ▶) T _min = 0.872, T _max = 0.892
24485 measured reflections
5417 independent reflections
4537 reflections with I > 2σ(I)
R _int = 0.026

Refinement

R[F ² > 2σ(F ²)] = 0.090
wR(F ²) = 0.306
S = 1.36
5417 reflections
328 parameters
H-atom parameters constrained
Δρ_max = 2.04 e Å⁻³
Δρ_min = −1.13 e Å⁻³

Data collection: X-AREA (Stoe & Cie, 2002 ▶); cell refinement: X-AREA; data reduction: X-RED32 (Stoe & Cie, 2002 ▶); program(s) used to solve structure: SIR97 (Altomare 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/S1600536808029309/hb2793sup1.cif

e-64-o1955-sup1.cif^{(26.3KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808029309/hb2793Isup2.hkl

e-64-o1955-Isup2.hkl^{(259.8KB, 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
C9—H9⋯O4ⁱ	0.98	2.34	3.285 (3)	161
C12—H12⋯Cg1ⁱⁱ	0.93	2.65	3.567 (4)	168

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Symmetry codes: (i) Inline graphic ; (ii) . Cg1 is the centroid of the thiophene ring (S2/C18–C21).

Acknowledgments

The authors acknowledge the Faculty of Arts and Sciences, Ondokuz Mayıs University, Turkey, for the use of the Stoe IPDS 2 diffractometer (purchased under grant F.279 of the University Research Fund).

supplementary crystallographic information

Comment

The title compound, (I), was synthesized as part of a research project (Kandinska et al., 2006) seeking precursors for the production of new tetrahydroquinolone derivatives with biological activity (Rothweiler et al., 2008).

In the molecule of (I) (Fig.1), the benzene ring A (C10—C15) of 3,4-dihydroisoquinolinone ring system is essentially planar, with an r.m.s. deviation of 0.005 (3) Å for C11 and its other six-membered part is not planar [its Puckering parameters (Cremer & Pople, 1975) are Q_T = 0.444 (3) Å, θ = 118.4 (4) ° and φ = 93.4 (4) °]. The thiophene ring B (S2—C18—C21) is almost planar, with an r.m.s. deviation for fitted atoms of 0.004 Å. The rings C (C1—C6) and D (C24—C29) are almost planar, with an r.m.s. deviation for fitted atoms of 0.012 Å and 0.021 Å, respectively. The dihedral angles between the planes of these rings are A/B = 80.91 (16), A/C = 22.79 (18), A/D = 9.9 (2), B/C = 80.73 (19), B/D = 88.9 (2) and C/D = 29.9 (2)°. An interesting feature of the crystal structure is the long C18—C19 bond of 1.594 (3) Å.

The crystal structure of (I) is stabilized by weak intra- and intermolecular C—H···O hydrogen bonds and C—H···π interactions (Table 1 and Fig. 2).

Experimental

Compound(I) was synthesized by reaction between trans-rac-4-(hydroxymethyl)-2-phenethyl-3-(thiophen-2-yl)-3,4-\ dihydroisoquinolin-1(2H)-one (5.91 g, 0.0163 mol) and 4-methylbenzene-1-sulfonyl chloride (6.22 g, 0.033 mol) in the presence of Et₃N (6.8 ml, 0.049 mol) in CH₂Cl₂. After working up the reaction mixture, compound (I) crystallized as colourless prisms from hexane–ethyl acetate (9:1 v/v) (yield 7.5 g, 89%; m.p. 385–386 K). Elemental analysis, calculated for C₂₉H₂₇NO₄S₂: C 67.29, H 5.26°; found: C 66.90, H 5.45°. IR (KBr) 3000 cm^-1 (C—H), 1647 cm-1 (C=O), 1603 cm-1 (ArH), 1467 cm^-1 (ArH), 1358 cm^-1 (S=O), 1172 cm^-1 (S=O). ¹H NMR (250 MHz, CDCl₃) δ (p.p.m.) = 2.32 (s, 3H, Ph—CH₃), 2.69 (t, 2H, J = 8.3 Hz, Ph—CH₂), 3.05–3.17 (m, 1H, N—CH₂^a), 3.45–3.54 (ddd, 1H, J = 1.3, 5.1 and 10 Hz, -OCH₂—CH), 3.69 (t, 1H, J = 10.3 Hz, -SO₃—CH₂^a), 4.04–4.23 (m, 2H, -SO₃—CH₂^b& N—CH₂^b), 5.10 (d, 1H, J = 0.8 Hz, Th—CH), 6.81 (dd, 1H, J = 3.5 and 4.9 Hz, Th-H), 6.76–6.81 (m, 1H, Ph-H), 7.06 (dd, 1H, J = 1.4 and 4.9 Hz, Th-H), 7.10–7.16 (m, 1H, Ph-H), 7.17–7.23 (m, 3H, H-Ph), 7.24–7.28 (m, 2H, Th-H, Ph-H), 7.28–7.33 (m, 2H, Ph-H), 7.40–7.48 (m, 2H, Ph-H), 7.78 (d, 2H, J = 8.3, Ph-H), 8.08–8.15 (m, 1H, Ph-H). ¹³C NMR (63 MHz, CDCl₃) δ = 162.8, 145.4, 142.7, 138.4,133.4, 132.6, 132.4, 130.1, 129.0, 128.8, 128.7, 128.5, 128.4, 127.8, 126.5,126.4, 125.6, 125.1, 70.0, 56.8, 48.5, 45.8, 34.1, 21.5.