3-Hydr­oxy-5,5-dimethyl-2-(2-oxo­propyl)cyclo­hex-2-enone

Martínez, R.; Hernández-Ortega, S.; Triana, L.; Camacho, J.

doi:10.1107/S1600536809049046

organic compounds

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ISSN: 2056-9890

Volume 65| Part 12| December 2009| Page o3186

doi:10.1107/S1600536809049046

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3-Hydroxy-5,5-dimethyl-2-(2-oxopropyl)cyclohex-2-enone

Roberto Martínez,^a ^* Simón Hernández-Ortega,^a ^* Liz Triana ^a and Jose Camacho ^b

^aInstituto de Química, Universidad Nacional Autónoma de México, Circuito Exterior, Ciudad Universitaria, México 04510, Mexico, and ^bLaboratorio 223, Departamento de Química, Universidad Simón Bolívar (USB), Apartado 47206, Caracas 1080-A, Venezuela
^*Correspondence e-mail: robmar@unam.mx, simonho@unam.mx

(Received 10 November 2009; accepted 17 November 2009; online 25 November 2009)

The title compound, C₁₁H₁₆O₃, was obtained by reaction of dimedone, 5,5-dimethylcyclohexane-1,3-dione, and α-chloroacetone. The cyclohexenone ring exhibits an envelope conformation with puckering amplitudes Q = 0.433 (2) and Φ = −109.0 (3)°. The 2-oxopropyl fragment is almost perpendicular to the cyclohexanone ring [dihedral angle = 77.72 (8)°]. In the crystal, the molecules are linked to each other through O—H⋯O hydrogen bonding, building a chain parallel to the b axis.

Related literature

The title compound is used in the synthesis of heterocyclic compounds. For the general synthesis of various heterocyclic compounds, see: Knorr (1884 ); Paal (1885 ); Martínez et al. (1995 , 2002 , 2006 ). For related structures, see: Nagarajan et al. (1986 ); Schaeffer & Vince (1962 ); Selvanayagam et al. (2003 ). For puckering parameters, see: Cremer & Pople (1975 ).

Experimental

Crystal data

C₁₁H₁₆O₃
M_r = 196.24
Monoclinic, P 2₁ /c
a = 10.005 (3) Å
b = 13.633 (4) Å
c = 8.441 (2) Å
β = 105.352 (4)°
V = 1110.3 (5) Å³
Z = 4
Mo Kα radiation
μ = 0.08 mm⁻¹
T = 298 K
0.32 × 0.16 × 0.15 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: none
8977 measured reflections
2032 independent reflections
1573 reflections with I > 2σ(I)
R_int = 0.044

Refinement

R[F² > 2σ(F²)] = 0.045
wR(F²) = 0.126
S = 1.06
2032 reflections
134 parameters
1 restraint
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.22 e Å⁻³
Δρ_min = −0.19 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2—H2⋯O1ⁱ	0.877 (14)	1.692 (14)	2.5685 (16)	176.9 (18)
Symmetry code: (i) $[-x+2, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Data collection: SMART (Bruker, 1999 ); cell refinement: SAINT (Bruker, 1999); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ); program(s) used to refine structure: SHELXTL; molecular graphics: ORTEPIII (Burnett & Johnson, 1996 ), ORTEP-3 for Windows (Farrugia, 1997 ) and PLATON (Spek, 2009 ); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809049046/dn2511sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809049046/dn2511Isup2.hkl

checkCIF report

Comment top

1,4-dicarbonyl derivatives are important intermediates in organic chemistry, they have great utility in the synthesis of various heterocyclic compounds. The Paal-Knorr reaction (Knorr, 1884; Paal, 1885) uses 1,4-dicarbonyl compounds to obtain different types of molecules like pyrroles, furans or thiophenes. (Martínez et al., 1995, 2002, 2006).

In the title compound, The cyclohexenone ring adopt an envelope conformation with overall puckering amplitudes Q 0.433 (2) and Φ = -109.0 (3) (Cremer & Pople, 1975), with the keto-enol (O1—C1—C2—C3—O2) fragment planar and the acetonyl moiety is almost perpendicular to this plane making a dihedral angle of 77.72 (8) ° (Fig. 1). Distances and angles agree with values reported in related compounds ( Nagarajan et al., 1986; Schaeffer & Vince, 1962; Selvanayagam, et al., 2003)

In the crystal the molecules are linked to each other through O-H···O hydrogen bonding building a chain parallel to the b axis (Table 1).

Related literature top

For the general synthesis of various heterocyclic compounds, see: Knorr (1884); Paal (1885); Martínez et al. (1995, 2002, 2006). For related structures, see: Nagarajan et al. (1986); Schaeffer & Vince (1962); Selvanayagam et al. (2003). For structural discussion, see: Cremer & Pople (1975).

Experimental top

A slurry of dimedone (0.01 equiv), chloroketone (0.01 equiv), and anhydrous potassium carbonate (0.01 equiv) in chloroform was kept stirred at room temperature for 48 h. The mixture was filtered; the insoluble salts were dissolved in water and the filtered solution was made acidic with concentrated HCl. The precipitate was filtered off and washed with water. Yield 70%. The Melting point (uncorrected) was determined on a Melt-Tem II melting points apparatus: 406–407 K. (Martínez et al., 2006). The title compound (I) was obtained as suitable crystal for X-ray analysis after recrystallization of the solid from 1:1 Methanol-Ethyl Acetate mixture. ¹H NMR [200 MHz, CDCl₃, δ (p.p.m.)]: 9.0 (brs, 1H), 3.41 (s, 2H), 2.35 (s, 4H), 2.16 (s, 3H), 1.08 (s, 6H).

Computing details top

Data collection: SMART (Bruker, 1999); cell refinement: SAINT (Bruker, 1999); data reduction: SAINT (Bruker, 1999); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: ORTEPIII (Burnett & Johnson, 1996), ORTEP-3 for Windows (Farrugia, 1997) and PLATON (Spek, 2009); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. Molecular structure of (I) with the atom labeling scheme. Ellipsoids are drawn at the 30% probability level. H atoms are represented as small spheres of arbitrary radii.
	Fig. 2. Partial packing view showing the formation of infinite chains parallel to the b axis through O-H···O hydrogen bonds. H atoms not involved in hydrogen bondings have been omitted for clarity. H bonds are shown as dashed lines. [Symmetry codes: (i) -x+2, y-1/2, -z+1/2]

3-Hydroxy-5,5-dimethyl-2-(2-oxopropyl)cyclohex-2-enone top

Crystal data top

C₁₁H₁₆O₃	F(000) = 424
M_r = 196.24	D_x = 1.174 Mg m⁻³
Monoclinic, P2₁/c	Melting point: 406 K
Hall symbol: -P 2ybc	Mo Kα radiation, λ = 0.71073 Å
a = 10.005 (3) Å	Cell parameters from 4286 reflections
b = 13.633 (4) Å	θ = 2.5–25.3°
c = 8.441 (2) Å	µ = 0.08 mm⁻¹
β = 105.352 (4)°	T = 298 K
V = 1110.3 (5) Å³	Prism, colourless
Z = 4	0.32 × 0.16 × 0.15 mm

Data collection top

Bruker SMART CCD area-detector diffractometer	1573 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.044
Graphite monochromator	θ_max = 25.4°, θ_min = 2.6°
Detector resolution: 0.83 pixels mm^-1	h = −12→12
ω scans	k = −16→16
8977 measured reflections	l = −10→10
2032 independent reflections

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.045	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.126	w = 1/[σ²(F_o²) + (0.0704P)² + 0.0505P] where P = (F_o² + 2F_c²)/3
S = 1.06	(Δ/σ)_max = 0.001
2032 reflections	Δρ_max = 0.22 e Å⁻³
134 parameters	Δρ_min = −0.19 e Å⁻³
1 restraint	Extinction correction: SHELXTL (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.021 (5)

Crystal data top

C₁₁H₁₆O₃	V = 1110.3 (5) Å³
M_r = 196.24	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 10.005 (3) Å	µ = 0.08 mm⁻¹
b = 13.633 (4) Å	T = 298 K
c = 8.441 (2) Å	0.32 × 0.16 × 0.15 mm
β = 105.352 (4)°

Data collection top

Bruker SMART CCD area-detector diffractometer	1573 reflections with I > 2σ(I)
8977 measured reflections	R_int = 0.044
2032 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.045	1 restraint
wR(F²) = 0.126	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	Δρ_max = 0.22 e Å⁻³
2032 reflections	Δρ_min = −0.19 e Å⁻³
134 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	0.96277 (13)	0.77843 (7)	0.23295 (14)	0.0636 (4)
O2	0.92396 (12)	0.44317 (7)	0.16061 (14)	0.0577 (4)
H2	0.9653 (18)	0.3880 (11)	0.199 (2)	0.069*
O3	0.68935 (15)	0.65312 (12)	0.26209 (17)	0.0924 (5)
C1	1.00978 (16)	0.69523 (9)	0.27353 (17)	0.0457 (4)
C2	0.94081 (15)	0.61103 (9)	0.18949 (17)	0.0431 (4)
C3	0.99433 (15)	0.52082 (9)	0.23391 (17)	0.0422 (4)
C4	1.12691 (15)	0.50283 (10)	0.36178 (18)	0.0467 (4)
H4A	1.1757	0.4495	0.3255	0.056*
H4B	1.1055	0.4820	0.4622	0.056*
C5	1.22308 (15)	0.59193 (10)	0.39985 (17)	0.0473 (4)
C6	1.13588 (17)	0.68191 (11)	0.41453 (18)	0.0529 (4)
H6A	1.1069	0.6766	0.5151	0.064*
H6B	1.1935	0.7399	0.4234	0.064*
C7	0.80924 (16)	0.62619 (11)	0.05840 (18)	0.0510 (4)
H7A	0.8230	0.6794	−0.0119	0.061*
H7B	0.7901	0.5674	−0.0085	0.061*
C8	0.68542 (18)	0.64907 (12)	0.1183 (2)	0.0616 (5)
C9	0.5541 (2)	0.6657 (2)	−0.0119 (3)	0.1196 (10)
H9A	0.5341	0.6094	−0.0824	0.179*
H9B	0.5639	0.7224	−0.0754	0.179*
H9C	0.4796	0.6762	0.0382	0.179*
C10	1.29416 (18)	0.60741 (12)	0.26238 (19)	0.0609 (5)
H10A	1.2252	0.6147	0.1596	0.091*
H10B	1.3516	0.5518	0.2568	0.091*
H10C	1.3503	0.6655	0.2844	0.091*
C11	1.33259 (19)	0.57556 (14)	0.5624 (2)	0.0702 (5)
H11A	1.3837	0.5168	0.5555	0.105*
H11B	1.2880	0.5691	0.6496	0.105*
H11C	1.3948	0.6305	0.5844	0.105*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0798 (8)	0.0312 (6)	0.0775 (8)	0.0051 (5)	0.0171 (6)	0.0014 (5)
O2	0.0632 (8)	0.0335 (6)	0.0708 (7)	−0.0047 (5)	0.0083 (6)	−0.0065 (5)
O3	0.0792 (10)	0.1301 (13)	0.0747 (9)	0.0173 (9)	0.0326 (8)	0.0072 (8)
C1	0.0586 (9)	0.0313 (7)	0.0510 (8)	0.0022 (6)	0.0213 (7)	−0.0002 (6)
C2	0.0489 (9)	0.0356 (7)	0.0451 (8)	0.0023 (6)	0.0130 (7)	−0.0011 (6)
C3	0.0486 (8)	0.0330 (7)	0.0474 (8)	−0.0033 (6)	0.0171 (7)	−0.0039 (6)
C4	0.0524 (9)	0.0362 (7)	0.0527 (8)	0.0045 (6)	0.0162 (7)	0.0032 (6)
C5	0.0493 (9)	0.0441 (8)	0.0460 (8)	−0.0033 (6)	0.0086 (7)	−0.0012 (6)
C6	0.0665 (11)	0.0404 (8)	0.0509 (8)	−0.0057 (7)	0.0136 (8)	−0.0086 (6)
C7	0.0573 (10)	0.0442 (8)	0.0496 (8)	0.0046 (7)	0.0107 (7)	0.0000 (6)
C8	0.0595 (11)	0.0612 (10)	0.0649 (11)	0.0083 (8)	0.0183 (9)	0.0112 (8)
C9	0.0639 (14)	0.193 (3)	0.0988 (17)	0.0375 (16)	0.0157 (13)	0.0363 (18)
C10	0.0557 (10)	0.0657 (11)	0.0631 (10)	−0.0091 (8)	0.0188 (8)	−0.0028 (8)
C11	0.0639 (11)	0.0764 (12)	0.0604 (10)	−0.0016 (9)	−0.0008 (9)	0.0026 (9)

Geometric parameters (Å, º) top

O1—C1	1.2409 (16)	C6—H6A	0.9700
O2—C3	1.3298 (16)	C6—H6B	0.9700
O2—H2	0.877 (14)	C7—C8	1.490 (2)
O3—C8	1.2050 (19)	C7—H7A	0.9700
C1—C2	1.4276 (19)	C7—H7B	0.9700
C1—C6	1.499 (2)	C8—C9	1.491 (3)
C2—C3	1.3541 (18)	C9—H9A	0.9600
C2—C7	1.493 (2)	C9—H9B	0.9600
C3—C4	1.492 (2)	C9—H9C	0.9600
C4—C5	1.530 (2)	C10—H10A	0.9600
C4—H4A	0.9700	C10—H10B	0.9600
C4—H4B	0.9700	C10—H10C	0.9600
C5—C10	1.528 (2)	C11—H11A	0.9600
C5—C11	1.529 (2)	C11—H11B	0.9600
C5—C6	1.529 (2)	C11—H11C	0.9600

C3—O2—H2	111.8 (12)	C8—C7—C2	115.25 (13)
O1—C1—C2	119.99 (14)	C8—C7—H7A	108.5
O1—C1—C6	120.52 (13)	C2—C7—H7A	108.5
C2—C1—C6	119.45 (12)	C8—C7—H7B	108.5
C3—C2—C1	119.28 (13)	C2—C7—H7B	108.5
C3—C2—C7	122.51 (12)	H7A—C7—H7B	107.5
C1—C2—C7	118.19 (12)	O3—C8—C7	122.90 (16)
O2—C3—C2	118.19 (13)	O3—C8—C9	121.54 (17)
O2—C3—C4	117.74 (12)	C7—C8—C9	115.56 (16)
C2—C3—C4	124.07 (12)	C8—C9—H9A	109.5
C3—C4—C5	114.25 (11)	C8—C9—H9B	109.5
C3—C4—H4A	108.7	H9A—C9—H9B	109.5
C5—C4—H4A	108.7	C8—C9—H9C	109.5
C3—C4—H4B	108.7	H9A—C9—H9C	109.5
C5—C4—H4B	108.7	H9B—C9—H9C	109.5
H4A—C4—H4B	107.6	C5—C10—H10A	109.5
C10—C5—C11	109.57 (14)	C5—C10—H10B	109.5
C10—C5—C6	109.94 (12)	H10A—C10—H10B	109.5
C11—C5—C6	109.45 (12)	C5—C10—H10C	109.5
C10—C5—C4	110.09 (12)	H10A—C10—H10C	109.5
C11—C5—C4	109.51 (13)	H10B—C10—H10C	109.5
C6—C5—C4	108.26 (12)	C5—C11—H11A	109.5
C1—C6—C5	114.28 (11)	C5—C11—H11B	109.5
C1—C6—H6A	108.7	H11A—C11—H11B	109.5
C5—C6—H6A	108.7	C5—C11—H11C	109.5
C1—C6—H6B	108.7	H11A—C11—H11C	109.5
C5—C6—H6B	108.7	H11B—C11—H11C	109.5
H6A—C6—H6B	107.6

O1—C1—C2—C3	179.22 (13)	C3—C4—C5—C11	163.65 (13)
C6—C1—C2—C3	−3.0 (2)	C3—C4—C5—C6	44.38 (16)
O1—C1—C2—C7	−2.5 (2)	O1—C1—C6—C5	−150.70 (14)
C6—C1—C2—C7	175.23 (13)	C2—C1—C6—C5	31.5 (2)
C1—C2—C3—O2	176.08 (12)	C10—C5—C6—C1	69.73 (17)
C7—C2—C3—O2	−2.1 (2)	C11—C5—C6—C1	−169.88 (13)
C1—C2—C3—C4	−3.2 (2)	C4—C5—C6—C1	−50.56 (17)
C7—C2—C3—C4	178.68 (13)	C3—C2—C7—C8	102.90 (17)
O2—C3—C4—C5	161.35 (13)	C1—C2—C7—C8	−75.28 (18)
C2—C3—C4—C5	−19.4 (2)	C2—C7—C8—O3	−1.6 (2)
C3—C4—C5—C10	−75.82 (16)	C2—C7—C8—C9	179.14 (19)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2···O1ⁱ	0.88 (1)	1.69 (1)	2.5685 (16)	177 (2)

Symmetry code: (i) −x+2, y−1/2, −z+1/2.

Experimental details

Crystal data
Chemical formula	C₁₁H₁₆O₃
M_r	196.24
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	298
a, b, c (Å)	10.005 (3), 13.633 (4), 8.441 (2)
β (°)	105.352 (4)
V (Å³)	1110.3 (5)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.08
Crystal size (mm)	0.32 × 0.16 × 0.15

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	8977, 2032, 1573
R_int	0.044
(sin θ/λ)_max (Å⁻¹)	0.602

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.045, 0.126, 1.06
No. of reflections	2032
No. of parameters	134
No. of restraints	1
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.22, −0.19

Computer programs: SMART (Bruker, 1999), SAINT (Bruker, 1999), SHELXTL (Sheldrick, 2008), ORTEPIII (Burnett & Johnson, 1996), ORTEP-3 for Windows (Farrugia, 1997) and PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2···O1ⁱ	0.877 (14)	1.692 (14)	2.5685 (16)	176.9 (18)

Symmetry code: (i) −x+2, y−1/2, −z+1/2.

Acknowledgements

JC thanks the Decanato de Investigación y Desarrollo, Dirección de Desarrollo Profesoral Universidad Simón Bolívar, and FONACIT-S3–2009000393 for financial support.

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