1-Meth­oxy-4-methyl-9,10-anthraquinone

Osman, C.P.; Ahmad, R.; Ismail, N.H.; Awang, K.; Ng, S.W.

doi:10.1107/S1600536811041912

organic compounds

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ISSN: 2056-9890

Volume 67| Part 11| November 2011| Page o2973

doi:10.1107/S1600536811041912

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1-Methoxy-4-methyl-9,10-anthraquinone

Che Puteh Osman,^a Rohaya Ahmad,^a Nor Hadiani Ismail,^a Khalijah Awang ^b and Seik Weng Ng ^b,^c ^*

^aFaculty of Applied Sciences, Universiti Teknologi MARA, 40450 Shah Alam, Malaysia, ^bDepartment of Chemistry, University of Malaya, 50603 Kuala Lumpur, Malaysia, and ^cChemistry Department, Faculty of Science, King Abdulaziz University, PO Box 80203 Jeddah, Saudi Arabia
^*Correspondence e-mail: seikweng@um.edu.my

(Received 11 October 2011; accepted 11 October 2011; online 22 October 2011)

The non-H atoms of the title compound, C₁₆H₁₂O₃, lie approximately in a common plane (r.m.s. deviation = 0.032 Å). The methyl C atom is forced away from the carbonyl O atom which can be seen by the widened C_{fused ring}–C_benzene–C_methyl angle of 125.8 (2)°.

Related literature

For the synthesis, see: Bentley et al. (1907 ); Fischer & Ziegler (1913 ).

Experimental

Crystal data

C₁₆H₁₂O₃
M_r = 252.26
Monoclinic, P 2₁
a = 8.8808 (4) Å
b = 4.8940 (2) Å
c = 13.7792 (5) Å
β = 96.136 (4)°
V = 595.45 (4) Å³
Z = 2
Cu Kα radiation
μ = 0.79 mm⁻¹
T = 100 K
0.30 × 0.10 × 0.02 mm

Data collection

Agilent SuperNova Dual diffractometer with an Atlas detector
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2010 ) T_min = 0.797, T_max = 0.984
2343 measured reflections
1367 independent reflections
1317 reflections with I > 2σ(I)
R_int = 0.014

Refinement

R[F² > 2σ(F²)] = 0.036
wR(F²) = 0.108
S = 1.16
1367 reflections
173 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 0.19 e Å⁻³
Δρ_min = −0.18 e Å⁻³

Data collection: CrysAlis PRO (Agilent, 2010); 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: X-SEED (Barbour, 2001 ); software used to prepare material for publication: publCIF (Westrip, 2010 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811041912/bt5675sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811041912/bt5675Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536811041912/bt5675Isup3.cml

checkCIF report

Comment top

1-Methoxy-4-methyl-9,10-anthraquinone was reported more than a century ago (Bentley et al., 1907; Fischer & Ziegler, 1913). We have used a modification of the synthesis to prepare 1-hydroxy-4-methyl-9,10-anthraquinone, which was then methylated to yield the title compound (Scheme). The non-hydrogen atoms of 1-methyl-4-methoxy-9,10-anthraquinone lie on a plane (r.m.s. deviation 0.032Å). The methyl C atom is forced away from the by the carbonyl O atom that is four bonds removed (C_{fused ring}–C_benzene–C_methyl 125.8 (2) °].

Its isolation from plants has not been reported yet.

Related literature top

For the synthesis, see: Bentley et al. (1907); Fischer & Ziegler (1913).

Experimental top

Phthalic anhydride (1.00 g, 0.67 mmol) and p-cresol (1.63 g, 1.50 mmol) were heated in a mixture of aluminium chloride (45 g) and sodium chloride (9 g) heated to 423–443 K for an hour. The reaction mixture turned deep red. Water (500 ml) containing concentrated hydrochloric acid (15 ml) was added. The product was collected and washed with saturated sodium bicarbonate, and was next purified by medium-pressure liquid chromatography (hexane: ethyl acetate) to give 1-hydroxy-4-methyl-9,10-anthroquinone (60% yield).

In the subsequent methylation reaction, 1-hydroxy-4-methyl-9,10-anthraquinone (1 mmol) and methyl iodide (1.5 mmol) along with potassium carbonate (1 mmol) were heated in acetone (30 ml) for 24 h. The solvent was removed and the product dissolved in dichloromethane. The solution was extraced with water. The organic layer was purified by medium-pressure liquid chromatography (hexane: ethyl acetate) to give the pure title compound (80% yield). Crystals were obtained by using methanol as solvent for recrystallization. The formulation was established by proton and carbon-13 NMR spectroscopy.

Computing details top

Data collection: CrysAlis PRO (Agilent, 2010); cell refinement: CrysAlis PRO (Agilent, 2010); data reduction: CrysAlis PRO (Agilent, 2010); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures top

Fig. 1. Anisotropic displacement ellipsoid plot (Barbour, 2001) of C₁₆H₁₂O₃ at the 70% probability level; hydrogen atoms are drawn as spheres of arbitrary radius.

1-Methoxy-4-methyl-9,10-anthraquinone top

Crystal data top

C₁₆H₁₂O₃	F(000) = 264
M_r = 252.26	D_x = 1.407 Mg m⁻³
Monoclinic, P2₁	Cu Kα radiation, λ = 1.54184 Å
Hall symbol: P 2yb	Cell parameters from 1483 reflections
a = 8.8808 (4) Å	θ = 3.2–76.1°
b = 4.8940 (2) Å	µ = 0.79 mm⁻¹
c = 13.7792 (5) Å	T = 100 K
β = 96.136 (4)°	Plate, orange
V = 595.45 (4) Å³	0.30 × 0.10 × 0.02 mm
Z = 2

Data collection top

Agilent SuperNova Dual diffractometer with an Atlas detector	1367 independent reflections
Radiation source: SuperNova (Cu) X-ray Source	1317 reflections with I > 2σ(I)
Mirror monochromator	R_int = 0.014
Detector resolution: 10.4041 pixels mm^-1	θ_max = 76.3°, θ_min = 3.2°
ω scans	h = −7→11
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2010)	k = −5→6
T_min = 0.797, T_max = 0.984	l = −17→17
2343 measured reflections

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)] = 0.036	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.108	H-atom parameters constrained
S = 1.16	w = 1/[σ²(F_o²) + (0.0706P)² + 0.0361P] where P = (F_o² + 2F_c²)/3
1367 reflections	(Δ/σ)_max = 0.001
173 parameters	Δρ_max = 0.19 e Å⁻³
1 restraint	Δρ_min = −0.18 e Å⁻³

Crystal data top

C₁₆H₁₂O₃	V = 595.45 (4) Å³
M_r = 252.26	Z = 2
Monoclinic, P2₁	Cu Kα radiation
a = 8.8808 (4) Å	µ = 0.79 mm⁻¹
b = 4.8940 (2) Å	T = 100 K
c = 13.7792 (5) Å	0.30 × 0.10 × 0.02 mm
β = 96.136 (4)°

Data collection top

Agilent SuperNova Dual diffractometer with an Atlas detector	1367 independent reflections
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2010)	1317 reflections with I > 2σ(I)
T_min = 0.797, T_max = 0.984	R_int = 0.014
2343 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.036	1 restraint
wR(F²) = 0.108	H-atom parameters constrained
S = 1.16	Δρ_max = 0.19 e Å⁻³
1367 reflections	Δρ_min = −0.18 e Å⁻³
173 parameters

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

	x	y	z	U_iso*/U_eq
O1	0.55994 (14)	0.5010 (4)	0.81572 (9)	0.0371 (4)
O2	0.66956 (14)	0.8795 (3)	0.93147 (9)	0.0317 (3)
O3	1.07132 (15)	0.4573 (4)	0.64116 (10)	0.0390 (4)
C1	0.67730 (18)	0.5016 (4)	0.77647 (11)	0.0248 (4)
C2	0.69140 (19)	0.3128 (4)	0.69352 (11)	0.0240 (4)
C3	0.5701 (2)	0.1401 (5)	0.66264 (12)	0.0291 (4)
H3	0.4802	0.1455	0.6943	0.035*
C4	0.5813 (2)	−0.0384 (5)	0.58604 (13)	0.0323 (4)
H4	0.4992	−0.1568	0.5655	0.039*
C5	0.7123 (2)	−0.0457 (5)	0.53870 (13)	0.0324 (4)
H5	0.7185	−0.1666	0.4853	0.039*
C6	0.8330 (2)	0.1223 (5)	0.56916 (11)	0.0300 (4)
H6	0.9226	0.1160	0.5372	0.036*
C7	0.82303 (19)	0.3018 (4)	0.64715 (11)	0.0247 (4)
C8	0.95447 (19)	0.4775 (4)	0.68049 (12)	0.0264 (4)
C9	0.94200 (19)	0.6767 (4)	0.76192 (11)	0.0235 (4)
C10	1.06468 (19)	0.8520 (4)	0.79051 (12)	0.0285 (4)
C11	1.0481 (2)	1.0335 (4)	0.86625 (13)	0.0304 (4)
H11	1.1295	1.1535	0.8865	0.037*
C12	0.9187 (2)	1.0470 (4)	0.91328 (13)	0.0280 (4)
H12	0.9124	1.1755	0.9643	0.034*
C13	0.79734 (18)	0.8729 (4)	0.88619 (11)	0.0250 (4)
C14	0.80695 (18)	0.6854 (4)	0.80882 (11)	0.0233 (4)
C15	1.2125 (2)	0.8622 (6)	0.74564 (15)	0.0400 (5)
H15A	1.1927	0.9088	0.6763	0.060*
H15B	1.2622	0.6833	0.7524	0.060*
H15C	1.2786	1.0010	0.7791	0.060*
C16	0.6594 (2)	1.0809 (5)	1.00589 (13)	0.0334 (4)
H16A	0.5623	1.0618	1.0330	0.050*
H16B	0.6663	1.2637	0.9777	0.050*
H16C	0.7425	1.0549	1.0578	0.050*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0319 (6)	0.0462 (9)	0.0358 (7)	−0.0103 (7)	0.0162 (5)	−0.0114 (7)
O2	0.0325 (6)	0.0349 (8)	0.0297 (6)	−0.0025 (6)	0.0130 (5)	−0.0066 (6)
O3	0.0362 (7)	0.0443 (9)	0.0403 (7)	−0.0043 (7)	0.0218 (6)	−0.0053 (7)
C1	0.0282 (7)	0.0262 (9)	0.0213 (7)	−0.0011 (8)	0.0086 (6)	0.0027 (8)
C2	0.0290 (8)	0.0234 (9)	0.0198 (7)	0.0005 (8)	0.0039 (6)	0.0035 (7)
C3	0.0328 (8)	0.0297 (10)	0.0249 (7)	−0.0020 (9)	0.0040 (6)	0.0031 (8)
C4	0.0390 (9)	0.0294 (10)	0.0274 (8)	−0.0019 (9)	−0.0019 (7)	−0.0005 (9)
C5	0.0439 (10)	0.0288 (10)	0.0241 (8)	0.0043 (10)	0.0019 (7)	−0.0019 (9)
C6	0.0377 (9)	0.0304 (10)	0.0226 (7)	0.0059 (9)	0.0070 (6)	0.0019 (8)
C7	0.0311 (8)	0.0240 (9)	0.0197 (7)	0.0029 (8)	0.0065 (6)	0.0051 (7)
C8	0.0310 (8)	0.0261 (9)	0.0239 (7)	0.0013 (9)	0.0107 (6)	0.0050 (9)
C9	0.0271 (7)	0.0222 (9)	0.0220 (7)	0.0009 (8)	0.0064 (6)	0.0064 (8)
C10	0.0273 (8)	0.0301 (10)	0.0286 (8)	−0.0005 (8)	0.0055 (6)	0.0064 (8)
C11	0.0300 (8)	0.0294 (11)	0.0316 (9)	−0.0050 (8)	0.0018 (7)	0.0021 (8)
C12	0.0333 (8)	0.0260 (10)	0.0245 (7)	0.0011 (8)	0.0018 (6)	0.0003 (8)
C13	0.0276 (8)	0.0258 (9)	0.0222 (7)	0.0029 (8)	0.0060 (6)	0.0042 (8)
C14	0.0262 (7)	0.0232 (9)	0.0212 (7)	0.0007 (7)	0.0056 (6)	0.0036 (7)
C15	0.0322 (9)	0.0474 (13)	0.0420 (10)	−0.0088 (10)	0.0107 (8)	−0.0021 (11)
C16	0.0387 (9)	0.0321 (11)	0.0309 (8)	0.0016 (9)	0.0105 (7)	−0.0045 (8)

Geometric parameters (Å, º) top

O1—C1	1.224 (2)	C8—C9	1.499 (3)
O2—C13	1.3526 (18)	C9—C10	1.409 (3)
O2—C16	1.432 (2)	C9—C14	1.422 (2)
O3—C8	1.225 (2)	C10—C11	1.390 (3)
C1—C2	1.485 (2)	C10—C15	1.511 (2)
C1—C14	1.491 (3)	C11—C12	1.380 (2)
C2—C7	1.392 (2)	C11—H11	0.9500
C2—C3	1.399 (3)	C12—C13	1.393 (3)
C3—C4	1.382 (3)	C12—H12	0.9500
C3—H3	0.9500	C13—C14	1.416 (2)
C4—C5	1.394 (3)	C15—H15A	0.9800
C4—H4	0.9500	C15—H15B	0.9800
C5—C6	1.380 (3)	C15—H15C	0.9800
C5—H5	0.9500	C16—H16A	0.9800
C6—C7	1.398 (3)	C16—H16B	0.9800
C6—H6	0.9500	C16—H16C	0.9800
C7—C8	1.483 (3)

C13—O2—C16	117.84 (15)	C11—C10—C9	117.28 (16)
O1—C1—C2	118.97 (17)	C11—C10—C15	116.89 (18)
O1—C1—C14	122.39 (16)	C9—C10—C15	125.83 (18)
C2—C1—C14	118.64 (14)	C12—C11—C10	122.90 (18)
C7—C2—C3	119.60 (17)	C12—C11—H11	118.6
C7—C2—C1	121.43 (15)	C10—C11—H11	118.6
C3—C2—C1	118.96 (15)	C11—C12—C13	120.28 (18)
C4—C3—C2	119.89 (17)	C11—C12—H12	119.9
C4—C3—H3	120.1	C13—C12—H12	119.9
C2—C3—H3	120.1	O2—C13—C12	121.67 (16)
C3—C4—C5	120.35 (18)	O2—C13—C14	118.93 (15)
C3—C4—H4	119.8	C12—C13—C14	119.39 (15)
C5—C4—H4	119.8	C13—C14—C9	118.89 (15)
C6—C5—C4	120.18 (18)	C13—C14—C1	120.61 (14)
C6—C5—H5	119.9	C9—C14—C1	120.49 (15)
C4—C5—H5	119.9	C10—C15—H15A	109.5
C5—C6—C7	119.78 (17)	C10—C15—H15B	109.5
C5—C6—H6	120.1	H15A—C15—H15B	109.5
C7—C6—H6	120.1	C10—C15—H15C	109.5
C2—C7—C6	120.19 (17)	H15A—C15—H15C	109.5
C2—C7—C8	120.47 (16)	H15B—C15—H15C	109.5
C6—C7—C8	119.34 (15)	O2—C16—H16A	109.5
O3—C8—C7	119.47 (18)	O2—C16—H16B	109.5
O3—C8—C9	121.16 (18)	H16A—C16—H16B	109.5
C7—C8—C9	119.36 (14)	O2—C16—H16C	109.5
C10—C9—C14	121.24 (16)	H16A—C16—H16C	109.5
C10—C9—C8	119.22 (15)	H16B—C16—H16C	109.5
C14—C9—C8	119.54 (15)

O1—C1—C2—C7	−179.01 (17)	C14—C9—C10—C11	0.0 (3)
C14—C1—C2—C7	1.1 (2)	C8—C9—C10—C11	179.94 (16)
O1—C1—C2—C3	0.0 (3)	C14—C9—C10—C15	−179.51 (18)
C14—C1—C2—C3	−179.87 (16)	C8—C9—C10—C15	0.5 (3)
C7—C2—C3—C4	−0.5 (3)	C9—C10—C11—C12	0.1 (3)
C1—C2—C3—C4	−179.55 (17)	C15—C10—C11—C12	179.60 (18)
C2—C3—C4—C5	−0.6 (3)	C10—C11—C12—C13	0.5 (3)
C3—C4—C5—C6	1.1 (3)	C16—O2—C13—C12	2.8 (3)
C4—C5—C6—C7	−0.6 (3)	C16—O2—C13—C14	−176.68 (15)
C3—C2—C7—C6	1.0 (3)	C11—C12—C13—O2	179.38 (16)
C1—C2—C7—C6	−179.92 (16)	C11—C12—C13—C14	−1.1 (3)
C3—C2—C7—C8	−178.30 (16)	O2—C13—C14—C9	−179.34 (15)
C1—C2—C7—C8	0.7 (3)	C12—C13—C14—C9	1.1 (2)
C5—C6—C7—C2	−0.5 (3)	O2—C13—C14—C1	1.1 (2)
C5—C6—C7—C8	178.84 (17)	C12—C13—C14—C1	−178.41 (16)
C2—C7—C8—O3	177.22 (17)	C10—C9—C14—C13	−0.6 (2)
C6—C7—C8—O3	−2.1 (3)	C8—C9—C14—C13	179.45 (16)
C2—C7—C8—C9	−2.7 (3)	C10—C9—C14—C1	178.98 (16)
C6—C7—C8—C9	177.98 (16)	C8—C9—C14—C1	−1.0 (2)
O3—C8—C9—C10	2.9 (3)	O1—C1—C14—C13	−1.3 (3)
C7—C8—C9—C10	−177.18 (16)	C2—C1—C14—C13	178.62 (15)
O3—C8—C9—C14	−177.11 (16)	O1—C1—C14—C9	179.17 (18)
C7—C8—C9—C14	2.8 (2)	C2—C1—C14—C9	−0.9 (2)

Experimental details

Crystal data
Chemical formula	C₁₆H₁₂O₃
M_r	252.26
Crystal system, space group	Monoclinic, P2₁
Temperature (K)	100
a, b, c (Å)	8.8808 (4), 4.8940 (2), 13.7792 (5)
β (°)	96.136 (4)
V (Å³)	595.45 (4)
Z	2
Radiation type	Cu Kα
µ (mm⁻¹)	0.79
Crystal size (mm)	0.30 × 0.10 × 0.02

Data collection
Diffractometer	Agilent SuperNova Dual diffractometer with an Atlas detector
Absorption correction	Multi-scan (CrysAlis PRO; Agilent, 2010)
T_min, T_max	0.797, 0.984
No. of measured, independent and observed [I > 2σ(I)] reflections	2343, 1367, 1317
R_int	0.014
(sin θ/λ)_max (Å⁻¹)	0.630

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.036, 0.108, 1.16
No. of reflections	1367
No. of parameters	173
No. of restraints	1
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.19, −0.18

Computer programs: CrysAlis PRO (Agilent, 2010), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), X-SEED (Barbour, 2001), publCIF (Westrip, 2010).

Acknowledgements

We thank the University of Malaya for supporting this study.

References

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