3-Dimethyl­amino-1-(4-methyl­phen­yl)prop-2-en-1-one

Deng, J.; Shen, D.; Zhou, Z.

doi:10.1107/S1600536809048879

organic compounds

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ISSN: 2056-9890

Volume 66| Part 1| January 2010| Page o2

doi:10.1107/S1600536809048879

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3-Dimethylamino-1-(4-methylphenyl)prop-2-en-1-one

Juean Deng,^a Dongsheng Shen ^a ^* and Zongzhou Zhou ^a

^aCollege of Chemistry and Chemical Engineering, Guangdong Pharmaceutical University, Guangzhou 510006, People's Republic of China
^*Correspondence e-mail: sds8@163.com

(Received 2 November 2009; accepted 17 November 2009; online 4 December 2009)

In the title compound, C₁₂H₁₅NO, the C=C and C=O functional groups and the benzene ring are involved in an extended conjugated system. The molecules are essentially planar with a maximal deviation from planarity for the non-H atoms of 0.062 (2) Å.

Related literature

For the pharmaceutical activity of enaminones, see: Edafiogh et al. (2003 ); Eddington et al. (2003 ). For the use of enaminones as chelating ligands for main group metals and transition metals in coordination chemistry, see: Cindrić et al. (2004 ); Shi et al. (2008 ). For the chemical synthesis of enaminones, see: Kantevari et al. (2007 ); Ke et al. (2009 ). For the crystal structures of enaminones, see: Lemmerer et al. (2007 ); Bertolasi et al. (1999 ); Blake et al. (1996 ).

Experimental

Crystal data

C₁₂H₁₅NO
M_r = 189.25
Monoclinic, P 2₁ /c
a = 8.7918 (17) Å
b = 5.9506 (12) Å
c = 20.789 (4) Å
β = 99.300 (3)°
V = 1073.3 (4) Å³
Z = 4
Mo Kα radiation
μ = 0.07 mm⁻¹
T = 173 K
0.08 × 0.06 × 0.03 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2004 ) T_min = 0.994, T_max = 0.998
5180 measured reflections
2290 independent reflections
1731 reflections with I > 2σ(I)
R_int = 0.023

Refinement

R[F² > 2σ(F²)] = 0.046
wR(F²) = 0.150
S = 1.02
2290 reflections
130 parameters
H-atom parameters constrained
Δρ_max = 0.27 e Å⁻³
Δρ_min = −0.23 e Å⁻³

Data collection: APEX2 (Bruker, 2005 ); cell refinement: SAINT-Plus (Bruker, 2005); data reduction: SAINT-Plus; 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.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809048879/vm2013sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809048879/vm2013Isup2.hkl

checkCIF report

Comment top

Enaminones and their metal complexes have been widely studied due to their applications in the fields of optical chemistry, medicinal chemistry and biotechnology. Those ligands are versatile synthetic intermediates that combine the ambident nucleophilicity of enamines with the ambident electrophilicity of enones and have been extensively used for the preparation of a variety of heterocyclic systems including some natural products and analogues. Moreover, in coordination chemistry, enaminones can be used as good chelating ligands for main group metals and transition metals (Cindrić et al., 2004; Shi et al.,2008). We report here the synthesis and structure of the title compound. The molecular structure of the title compound is shown in Fig.1. The molecule crystallized as an E isomer with extended conjugation involving N, C=C, C=O, and the benzene ring. As a consequence the molecule is planar, the maximal deviation from planarity for the non-hydrogen atoms is 0.062 (2) Å.

Related literature top

For the pharmaceutical activity of enaminones, see: Edafiogh et al. (2003); Eddington et al. (2003). For the use of enaminones as chelating ligands for main group metals and transition metals in coordination chemistry, see: Cindrić et al. (2004); Shi et al. (2008). For the chemical synthesis of enaminones, see: Kantevari et al. (2007); Ke et al. (2009). For the crystal structures of enaminones, see: Lemmerer et al. (2007); Bertolasi et al. (1999); Blake et al. (1996).

Experimental top

A solution of 4-Methylacetophenone (13.2 g, 0.1 mol) in ethyl formate (14.8 g, 0.2 mol) was added dropwise to a stirred suspension of sodium ethoxide(6.8 g, 0.1 mol) in anhydrous diethyl ether (50 ml) at room temperature. After stirring for 4 h, 8.8 g Dimethylamine hydrochloride (0.11 mol) in 20 ml water was added dropwise to the stirred suspended matter, and it was stirred for another 2 h. Then, the organic phase was separated, and the solvent was removed on a rotary evaporator, the residual was recrystallized in hexane-acetone (10:1) in an afford of the title compound (15.2 g). Crystals were obtained by slow evaporation of a solution in diethyl ether at room temperature.

Computing details top

Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT-Plus (Bruker, 2005); data reduction: SAINT-Plus (Bruker, 2005); 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 (Sheldrick, 2008).

Figures top

Fig. 1. The structure of the title compound, with displacement ellipsoids at the 30% probability level.

3-Dimethylamino-1-(4-methylphenyl)prop-2-en-1-one top

Crystal data top

C₁₂H₁₅NO	F(000) = 408
M_r = 189.25	D_x = 1.171 Mg m⁻³
Monoclinic, P2₁/c	Melting point: 367 K
Hall symbol: -P 2ybc	Mo Kα radiation, λ = 0.71073 Å
a = 8.7918 (17) Å	Cell parameters from 1291 reflections
b = 5.9506 (12) Å	θ = 3.1–28.6°
c = 20.789 (4) Å	µ = 0.07 mm⁻¹
β = 99.300 (3)°	T = 173 K
V = 1073.3 (4) Å³	Plate, colourless
Z = 4	0.08 × 0.06 × 0.03 mm

Data collection top

Bruker APEX CCD diffractometer	2290 independent reflections
Radiation source: fine-focus sealed tube	1731 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.023
ω and phi scans	θ_max = 27.0°, θ_min = 2.0°
Absorption correction: multi-scan (SADABS; Sheldrick, 2004)	h = −10→10
T_min = 0.994, T_max = 0.998	k = −7→7
5180 measured reflections	l = −11→26

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.046	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.150	H-atom parameters constrained
S = 1.02	w = 1/[σ²(F_o²) + (0.0918P)² + 0.1894P] where P = (F_o² + 2F_c²)/3
2290 reflections	(Δ/σ)_max < 0.001
130 parameters	Δρ_max = 0.27 e Å⁻³
0 restraints	Δρ_min = −0.23 e Å⁻³

Crystal data top

C₁₂H₁₅NO	V = 1073.3 (4) Å³
M_r = 189.25	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 8.7918 (17) Å	µ = 0.07 mm⁻¹
b = 5.9506 (12) Å	T = 173 K
c = 20.789 (4) Å	0.08 × 0.06 × 0.03 mm
β = 99.300 (3)°

Data collection top

Bruker APEX CCD diffractometer	2290 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 2004)	1731 reflections with I > 2σ(I)
T_min = 0.994, T_max = 0.998	R_int = 0.023
5180 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.046	0 restraints
wR(F²) = 0.150	H-atom parameters constrained
S = 1.02	Δρ_max = 0.27 e Å⁻³
2290 reflections	Δρ_min = −0.23 e Å⁻³
130 parameters

Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
O1	0.19626 (13)	0.51500 (19)	0.07917 (6)	0.0490 (4)
N1	−0.15817 (14)	0.0530 (2)	0.05528 (6)	0.0327 (3)
C1	0.84154 (18)	0.1518 (3)	0.24118 (8)	0.0439 (4)
H1A	0.8475	−0.0002	0.2596	0.066*
H1B	0.8626	0.2619	0.2765	0.066*
H1C	0.9179	0.1680	0.2120	0.066*
C2	0.68222 (16)	0.1912 (2)	0.20336 (7)	0.0308 (3)
C3	0.64246 (17)	0.3950 (3)	0.17274 (7)	0.0346 (4)
H3A	0.7179	0.5101	0.1744	0.042*
C4	0.49477 (17)	0.4341 (2)	0.13971 (7)	0.0318 (3)
H4A	0.4705	0.5753	0.1193	0.038*
C5	0.38156 (16)	0.2684 (2)	0.13621 (6)	0.0271 (3)
C6	0.42232 (16)	0.0632 (2)	0.16573 (7)	0.0302 (3)
H6A	0.3478	−0.0535	0.1632	0.036*
C7	0.57032 (17)	0.0256 (3)	0.19896 (7)	0.0328 (4)
H7A	0.5952	−0.1161	0.2190	0.039*
C8	0.22148 (16)	0.3234 (2)	0.10167 (7)	0.0301 (3)
C9	0.10551 (16)	0.1520 (2)	0.09670 (7)	0.0291 (3)
H9A	0.1299	0.0087	0.1157	0.035*
C10	−0.03947 (16)	0.1940 (2)	0.06473 (7)	0.0296 (3)
H10A	−0.0578	0.3408	0.0472	0.036*
C11	−0.1441 (2)	−0.1751 (3)	0.07988 (9)	0.0442 (4)
H11A	−0.0440	−0.2368	0.0739	0.066*
H11B	−0.2268	−0.2675	0.0560	0.066*
H11C	−0.1520	−0.1752	0.1264	0.066*
C12	−0.30880 (17)	0.1211 (3)	0.02142 (8)	0.0411 (4)
H12A	−0.3026	0.2740	0.0045	0.062*
H12B	−0.3833	0.1175	0.0518	0.062*
H12C	−0.3421	0.0178	−0.0148	0.062*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0387 (7)	0.0328 (6)	0.0712 (9)	−0.0016 (5)	−0.0038 (6)	0.0170 (6)
N1	0.0276 (6)	0.0359 (7)	0.0341 (7)	−0.0024 (5)	0.0035 (5)	−0.0010 (5)
C1	0.0330 (9)	0.0542 (10)	0.0421 (9)	0.0026 (7)	−0.0008 (7)	−0.0023 (8)
C2	0.0276 (7)	0.0373 (8)	0.0274 (7)	0.0008 (6)	0.0047 (5)	−0.0040 (6)
C3	0.0325 (8)	0.0346 (8)	0.0367 (8)	−0.0090 (6)	0.0056 (6)	−0.0041 (6)
C4	0.0360 (8)	0.0261 (7)	0.0335 (8)	−0.0030 (6)	0.0065 (6)	0.0026 (6)
C5	0.0283 (7)	0.0286 (7)	0.0250 (7)	−0.0013 (5)	0.0062 (5)	−0.0018 (5)
C6	0.0299 (7)	0.0280 (7)	0.0326 (8)	−0.0030 (6)	0.0050 (6)	0.0013 (6)
C7	0.0356 (8)	0.0318 (8)	0.0309 (7)	0.0028 (6)	0.0048 (6)	0.0031 (6)
C8	0.0321 (8)	0.0280 (7)	0.0305 (7)	0.0006 (6)	0.0056 (6)	0.0015 (6)
C9	0.0286 (8)	0.0282 (7)	0.0307 (7)	0.0004 (6)	0.0055 (6)	0.0019 (6)
C10	0.0316 (8)	0.0288 (7)	0.0296 (7)	−0.0003 (6)	0.0083 (6)	−0.0007 (6)
C11	0.0457 (10)	0.0360 (9)	0.0512 (10)	−0.0103 (7)	0.0090 (8)	−0.0011 (7)
C12	0.0285 (8)	0.0562 (11)	0.0377 (8)	−0.0011 (7)	0.0031 (6)	−0.0056 (7)

Geometric parameters (Å, º) top

O1—C8	1.2388 (18)	C5—C8	1.509 (2)
N1—C10	1.3288 (18)	C6—C7	1.389 (2)
N1—C11	1.448 (2)	C6—H6A	0.9500
N1—C12	1.453 (2)	C7—H7A	0.9500
C1—C2	1.510 (2)	C8—C9	1.434 (2)
C1—H1A	0.9800	C9—C10	1.362 (2)
C1—H1B	0.9800	C9—H9A	0.9500
C1—H1C	0.9800	C10—H10A	0.9500
C2—C7	1.385 (2)	C11—H11A	0.9800
C2—C3	1.388 (2)	C11—H11B	0.9800
C3—C4	1.387 (2)	C11—H11C	0.9800
C3—H3A	0.9500	C12—H12A	0.9800
C4—C5	1.395 (2)	C12—H12B	0.9800
C4—H4A	0.9500	C12—H12C	0.9800
C5—C6	1.387 (2)

C10—N1—C11	121.29 (13)	C2—C7—C6	121.09 (13)
C10—N1—C12	121.85 (13)	C2—C7—H7A	119.5
C11—N1—C12	116.84 (13)	C6—C7—H7A	119.5
C2—C1—H1A	109.5	O1—C8—C9	123.07 (13)
C2—C1—H1B	109.5	O1—C8—C5	118.41 (13)
H1A—C1—H1B	109.5	C9—C8—C5	118.52 (12)
C2—C1—H1C	109.5	C10—C9—C8	120.19 (13)
H1A—C1—H1C	109.5	C10—C9—H9A	119.9
H1B—C1—H1C	109.5	C8—C9—H9A	119.9
C7—C2—C3	117.91 (13)	N1—C10—C9	127.35 (14)
C7—C2—C1	120.88 (14)	N1—C10—H10A	116.3
C3—C2—C1	121.21 (14)	C9—C10—H10A	116.3
C4—C3—C2	121.32 (13)	N1—C11—H11A	109.5
C4—C3—H3A	119.3	N1—C11—H11B	109.5
C2—C3—H3A	119.3	H11A—C11—H11B	109.5
C3—C4—C5	120.69 (14)	N1—C11—H11C	109.5
C3—C4—H4A	119.7	H11A—C11—H11C	109.5
C5—C4—H4A	119.7	H11B—C11—H11C	109.5
C6—C5—C4	117.92 (13)	N1—C12—H12A	109.5
C6—C5—C8	123.77 (13)	N1—C12—H12B	109.5
C4—C5—C8	118.31 (13)	H12A—C12—H12B	109.5
C5—C6—C7	121.06 (13)	N1—C12—H12C	109.5
C5—C6—H6A	119.5	H12A—C12—H12C	109.5
C7—C6—H6A	119.5	H12B—C12—H12C	109.5

Experimental details

Crystal data
Chemical formula	C₁₂H₁₅NO
M_r	189.25
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	173
a, b, c (Å)	8.7918 (17), 5.9506 (12), 20.789 (4)
β (°)	99.300 (3)
V (Å³)	1073.3 (4)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.07
Crystal size (mm)	0.08 × 0.06 × 0.03

Data collection
Diffractometer	Bruker APEX CCD diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 2004)
T_min, T_max	0.994, 0.998
No. of measured, independent and observed [I > 2σ(I)] reflections	5180, 2290, 1731
R_int	0.023
(sin θ/λ)_max (Å⁻¹)	0.639

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.046, 0.150, 1.02
No. of reflections	2290
No. of parameters	130
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.27, −0.23

Computer programs: APEX2 (Bruker, 2005), SAINT-Plus (Bruker, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Acknowledgements

The authors thank the Natural Science Research Plan Project of Guangdong Province for financial surpport (05552838).

References

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