1-[4-(2-Amino­anilino)phen­yl]-2,2,2-trifluoro­ethanone

Angelika Dorn; Dieter Schollmeyer; Stefan A Laufer

doi:10.1107/S1600536810008937

. 2010 Apr 24;66(Pt 5):o1149. doi: 10.1107/S1600536810008937

1-[4-(2-Aminoanilino)phenyl]-2,2,2-trifluoroethanone

Angelika Dorn ^a, Dieter Schollmeyer ^b, Stefan A Laufer ^a,^*

PMCID: PMC2979181 PMID: 21579196

Abstract

In the title compound, C₁₄H₁₁F₃N₂O, the two aromatic rings are oriented at a dihedral angle of 70.84 (8)°. The crystal structure displays intermolecular N—H⋯O and N—H⋯F interactions.

Related literature

For 2,2,2-trifluoroacetophenones as intermediates for further Buchwald–Hartwig coupling, see: Colard et al. (1994 ▶); Schenck et al. (2004 ▶).

Experimental

Crystal data

C₁₄H₁₁F₃N₂O
M _r = 280.25
Orthorhombic,
a = 13.0385 (13) Å
b = 8.7129 (7) Å
c = 22.424 (2) Å
V = 2547.4 (4) Å³
Z = 8
Mo Kα radiation
μ = 0.12 mm⁻¹
T = 173 K
0.4 × 0.3 × 0.2 mm

Data collection

Bruker SMART APEXII diffractometer
21134 measured reflections
3033 independent reflections
2498 reflections with I > 2σ(I)
R _int = 0.026

Refinement

R[F ² > 2σ(F ²)] = 0.045
wR(F ²) = 0.127
S = 1.06
3033 reflections
181 parameters
H-atom parameters constrained
Δρ_max = 0.67 e Å⁻³
Δρ_min = −0.29 e Å⁻³

Data collection: APEX2 (Bruker, 2006 ▶); cell refinement: SAINT (Bruker, 2006 ▶); data reduction: SAINT; program(s) used to solve structure: SIR97 (Altomare et al., 1999 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: PLATON (Spek, 2009 ▶); software used to prepare material for publication: PLATON.

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810008937/bt5212sup1.cif

e-66-o1149-sup1.cif^{(17.4KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810008937/bt5212Isup2.hkl

e-66-o1149-Isup2.hkl^{(148.9KB, 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
N7—H7B⋯F19ⁱ	0.91	2.32	3.2077 (19)	166
N8—H8⋯O16ⁱⁱ	0.96	2.06	2.9757 (17)	159

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

supplementary crystallographic information

Comment

2,2,2-Trifluoroacetophenones are well known as building-blocks in the synthesis of therapeutic agents for example as acetylcholinesterase inhibitors (Colard et al., 1994), as anticonvulsants (Schenck et al., 2004) or as hPPAR agonists. The title compound was prepared in the course of our studies on acetophenone derivatives as potent p38 mitogen-activated protein (MAP) kinase inhibitors.

In the molecule (Fig. 1), rings A (C1—C6) and B (C10—C15) are, of course, planar and they are oriented at a dihedral angle of A/B = 70.84 (8)°. In the crystal structure, intermolecular N8—H8···O16 (2,06 Å) and N7—H7B···F19 (2,32 Å) interactions link the molecules into a three dimensional network. The N8—H8···O16 hydrogen bond forms a chain along the a-axis whereas the N7—H7B···F19 interaction connects two of this chains in direction parallel to the c-axis.

Experimental

For the preparation of the title compound a mixture of 501 mg (2.4 mmol) 1-(4-chlorophenyl)-2,2,2-trifluoroethanone, 332 mg (2.4 mmol) 2-nitroaniline, 1400 mg (4.3 mmol) Cs₂CO₃,90 mg (0.19 mmol) 2-(dicyclohexylphosphino)-2'-, 4'-, 6'-triisopropylbiphenyl and 20 mg (0.09 mmol) Pd(OAc)₂ in 2 ml absolute tert-butanol and 8 ml absolute toluol was stirred for 2 h at 90 °C under an atmosphere of argon. The mixture was diluted with water then extracted with ethyl acetate. The extracts were combined, washed with saturated saline solution, and then dried over Na₂SO₄. The solvent was removed under vacuum and the crude product was dissolved in 10 ml ethanol, 840 mg (3.71 mmol) tin(II)chloride-dihydrate was added and stirred for 5 h at 348 K. After cooling down to room temperature the mixture was quenched with 20 ml ice-water and after alkalization with NaOH (20 %) extracted three-times with ethyl acetate. The combined organic layer was washed twice with water, dried (Na₂SO₄), and evaporated under reduced pressure. The residue was purified by flashchromatography (SiO₂ 60, hexane / ethyl acetate) (yield: 21.5 %). Crystals of the title compound were obtained by slow evaporation of a methanol d6solution at room temperature.