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ISSN: 2056-9890

Lacinilene C 7-methyl ether

aA.S. Sadykov Institute of Bioorganic Chemistry, Academy of Sciences of Uzbekistan, Mirzo Ulugbek str. 83, Tashkent 100125, Uzbekistan, and bSouthern Plains Agricultural Research Center, Agricultural Research Service, USDA, College Station, TX 77845, USA
*Correspondence e-mail: via74@yandex.ru

(Received 18 June 2013; accepted 1 August 2013; online 7 August 2013)

The title compound, C16H20O3 [systematic name: 1-hy­droxy-7-meth­oxy-1,6-dimethyl-4-(propan-2-yl)naphthalen-2(1H)-one], is a sesquiterpene isolated from foliar tissues of the cotton plant and is of inter­est with respect to its anti­bacterial properties. Its phenyl ring is ideally planar, and the maximum of deviation in the second ring is 0.386 (3) Å. The hy­droxy group and the methyl group are oriented in an equatorial fashion and axial, respectively, to the second ring. In the crystal, inversion dimers are formed through pairs of O—H⋯O hydrogen bonds. Weak C—H⋯O hydrogen bonds link the dimers into columns along the c axis. These columns form a crystal structure with a crystal packing factor of 0.66.

Related literature

For the original isolation from Ulmus laciniata Mayr and proposed structure, see: Suzuki et al. (1972[Suzuki, H., Yasuda, S. & Hanzawa, M. (1972). Mokuzai Gakkaishi, 18, 617-622.]). For isolation from cotton bracts (Gossypium), identification and structure definition, see: Stipanovic et al. (1975[Stipanovic, R. D., Wakelyn, P. J. & Bell, A. A. (1975). Phytochemistry, 14, 1041-1043.], 1981[Stipanovic, R. D., Greenblatt, G. A., Beier, R. C. & Bell, A. A. (1981). Phytochemistry, 20, 729-730.]). For information on the biological activity, see: Essenberg et al. (1982[Essenberg, M., Doherty, M. d'A., Hamilton, B. K., Henning, V. T., Cover, E. C., Mcfaul, S. J. & Johnson, W. M. (1982). Phytopathology, 72, 1349-1356.]). For biosynthetic studies, see: Stipanovic et al. (1981[Stipanovic, R. D., Greenblatt, G. A., Beier, R. C. & Bell, A. A. (1981). Phytochemistry, 20, 729-730.]); Essenberg et al. (1985[Essenberg, M., Stoessl, A. & Stothers, J. B. (1985). J. Chem. Soc. Chem. Commun. 9, 556-557.]).

[Scheme 1]

Experimental

Crystal data
  • C16H20O3

  • Mr = 260.32

  • Triclinic, [P \overline 1]

  • a = 8.285 (2) Å

  • b = 8.987 (2) Å

  • c = 10.665 (3) Å

  • α = 68.58 (2)°

  • β = 78.95 (2)°

  • γ = 88.87 (2)°

  • V = 724.4 (3) Å3

  • Z = 2

  • Cu Kα radiation

  • μ = 0.65 mm−1

  • T = 295 K

  • 0.34 × 0.27 × 0.20 mm

Data collection
  • Oxford Diffraction Xcalibur Ruby CCD diffractometer

  • Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009[Oxford Diffraction (2009). CrysAlis PRO and CrysAlis RED. Oxford Diffraction Ltd, Yarnton, England.]) Tmin = 0.809, Tmax = 0.878

  • 6210 measured reflections

  • 2927 independent reflections

  • 1928 reflections with I > 2σ(I)

  • Rint = 0.030

Refinement
  • R[F2 > 2σ(F2)] = 0.051

  • wR(F2) = 0.171

  • S = 1.06

  • 2927 reflections

  • 182 parameters

  • H atoms treated by a mixture of independent and constrained refinement

  • Δρmax = 0.18 e Å−3

  • Δρmin = −0.18 e Å−3

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA D—H⋯A
O3—H3⋯O2i 0.87 (3) 2.08 (3) 2.892 (2) 156.3
C13—H13B⋯O2ii 0.96 2.51 3.467 (2) 177
Symmetry codes: (i) -x+1, -y+1, -z+2; (ii) x, y, z-1.

Data collection: CrysAlis PRO (Oxford Diffraction, 2009[Oxford Diffraction (2009). CrysAlis PRO and CrysAlis RED. Oxford Diffraction Ltd, Yarnton, England.]); cell refinement: CrysAlis PRO; data reduction: CrysAlis RED (Oxford Diffraction, 2009[Oxford Diffraction (2009). CrysAlis PRO and CrysAlis RED. Oxford Diffraction Ltd, Yarnton, England.]); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: XP in SHELXTL (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); software used to prepare material for publication: SHELXL97.

Supporting information


Comment top

The title compound, C16H20O3, LCME is a sesquiterpene isolated from foliar tissues of the cotton plant. Its biosynthesis is induced in response to infection by the bacterial plant pathogen, Xanthomonas campestris pv. malvacearum; the latter is the causal agent of bacterial blight, and LCME exhibits antibacterial activity against this pathogen. LCME was originally isolated from Ulmus laciniata Mayr (Suzuki et al., 1972), but the proposed structure was incorrect. Subsequently, it was isolated together with lacinilene C from frost–killed cotton bracts (Gossypium species) and its structure was revised (Stipanovic et al., 1975). LCME is produced by autoxidation of 2–hydroxy–7–methoxycadalene, which also occurs in cotton plant foliage (Stipanovic et al., 1981). The biosynthesis was first elucidated by Essenberg et al. (1985). However, lacinilene C (the un–methylated derivative of lacinilene C 7–methyl ether) isolated from cotton tissues is optically active, which indicates it is the product of enzymatic transformation of 2,7–dihydroxycadalene (Essenberg et al., 1982). The conformation of the title molecule and numbering scheme of atoms is shown in Fig. 1. The atoms of the phenyl ring (C1–C4/C9/C10) are ideal planar with a r.m.s. = 0.0085 Å. In the second ring, the atoms C5–C7/C9/C10 lie in an ideal plane with a r.m.s. = 0.0313 Å, and the deviation from planarity of atom C8 is equal to 0.386 (3) Å. The dihedral angle between these planes is equal to 170.2 (1)°. The hydroxy group O3 and the methyl group C12 are oriented equatorially and axially to the second ring, respectively. In the crystal structure, the centrosymmetric dimers are formed through pairs of O3—H3···O2i classical hydrogen bonds. Weak non–classical hydrogen bonds between C13—H13B···O2ii of the centrosymmetric dimers associate into columns by translation along the c axis (Fig. 2). Symmetry codes: (i) -x+1,-y+1,-z+2; (ii) x, y, z-1. The columns form a crystal structure with a packing factor 0.66.

Related literature top

For the original isolation from Ulmus laciniata Mayr and proposed structure, see: Suzuki et al. (1972). For isolation from cotton bracts (Gossypium), identification and structure definition, see: Stipanovic et al. (1975, 1981). For information on the biological activity, see: Essenberg et al. (1982). For biosynthetic studies, see: Stipanovic et al. (1981); Essenberg et al. (1985).

Experimental top

The title compound was isolated from frost–killed cotton bracts (Gossypium species) by extraction and silica gel LC procedures as previously described (Stipanovic et al., 1981). For achieving separation of the closely related compounds, the partially purified fraction was further chromatographed by consecutive injections on semi–preparative RP–HPLC column (Agilent 1100 HPLC system; Zorbax Eclipse XDB C8 column 9.4× 250 mm, 5µm; Agilent Technologies Inc, USA). The column was eluted using a linear gradient of H2O (A) /CH3OH (B) (HPLC grade, Sigma–Aldrich, DE) from 60 to 90% B for 30 minutes at a flow rate of 3 ml/min with the following segment of 100% B within 5 minutes and eluates were monitored at 254 nm. Crystals were obtained by slow evaporation of the HPLC eluent, and the most appropriate for X-ray diffraction were collected (m.p. 57–60°C).

Refinement top

All H atoms were placed in geometrically idealized positions C—H = 0.98Å for methine H, C—H = 0.96Å for methyl H and C—H = 0.93Å for aromatic H and treated as riding on their parent atoms, with Uiso(H) = 1.5Ueq(C) for methyl H; Uiso(H) = 1.2Ueq(C) for aromatic and methine H. The H atom of hydroxy group was refined freely.

Computing details top

Data collection: CrysAlis PRO (Oxford Diffraction, 2009); cell refinement: CrysAlis PRO (Oxford Diffraction, 2009); data reduction: CrysAlis RED (Oxford Diffraction, 2009); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: XP in SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. The molecular structure of title compound, with the atom–numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. H atoms are presented as a small spheres of arbitrary radius.
[Figure 2] Fig. 2. A packing diagram for title compound.
1-Hydroxy-7-methoxy-1,6-dimethyl-4-(propan-2-yl)naphthalen-2(1H)-one top
Crystal data top
C16H20O3Z = 2
Mr = 260.32F(000) = 280
Triclinic, P1Dx = 1.194 Mg m3
a = 8.285 (2) ÅCu Kα radiation, λ = 1.54184 Å
b = 8.987 (2) ÅCell parameters from 602 reflections
c = 10.665 (3) Åθ = 4.5–77.4°
α = 68.58 (2)°µ = 0.65 mm1
β = 78.95 (2)°T = 295 K
γ = 88.87 (2)°Block, white
V = 724.4 (3) Å30.34 × 0.27 × 0.20 mm
Data collection top
Oxford Diffraction Xcalibur Ruby CCD
diffractometer
2927 independent reflections
Radiation source: fine–focus sealed tube1928 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.030
ω scansθmax = 75.9°, θmin = 4.5°
Absorption correction: multi-scan
(CrysAlis PRO; Oxford Diffraction, 2009)
h = 910
Tmin = 0.809, Tmax = 0.878k = 1011
6210 measured reflectionsl = 1313
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.051H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.171 w = 1/[σ2(Fo2) + (0.0933P)2 + 0.0437P]
where P = (Fo2 + 2Fc2)/3
S = 1.06(Δ/σ)max < 0.001
2927 reflectionsΔρmax = 0.18 e Å3
182 parametersΔρmin = 0.18 e Å3
0 restraintsExtinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.008 (2)
Crystal data top
C16H20O3γ = 88.87 (2)°
Mr = 260.32V = 724.4 (3) Å3
Triclinic, P1Z = 2
a = 8.285 (2) ÅCu Kα radiation
b = 8.987 (2) ŵ = 0.65 mm1
c = 10.665 (3) ÅT = 295 K
α = 68.58 (2)°0.34 × 0.27 × 0.20 mm
β = 78.95 (2)°
Data collection top
Oxford Diffraction Xcalibur Ruby CCD
diffractometer
2927 independent reflections
Absorption correction: multi-scan
(CrysAlis PRO; Oxford Diffraction, 2009)
1928 reflections with I > 2σ(I)
Tmin = 0.809, Tmax = 0.878Rint = 0.030
6210 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0510 restraints
wR(F2) = 0.171H atoms treated by a mixture of independent and constrained refinement
S = 1.06Δρmax = 0.18 e Å3
2927 reflectionsΔρmin = 0.18 e Å3
182 parameters
Special details top

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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 > 2σ(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
xyzUiso*/Ueq
O10.17788 (19)0.7003 (2)0.39017 (14)0.0736 (5)
O20.3720 (2)0.6105 (2)1.03293 (16)0.0881 (6)
O30.48189 (19)0.6395 (2)0.76954 (16)0.0745 (5)
C10.2611 (2)0.7114 (2)0.59257 (18)0.0557 (5)
H10.37100.70020.55880.067*
C20.1443 (3)0.7162 (2)0.51528 (18)0.0564 (5)
C30.0215 (3)0.7362 (3)0.56220 (19)0.0587 (5)
C40.0648 (2)0.7455 (2)0.69137 (19)0.0562 (5)
H40.17470.75740.72440.067*
C50.0011 (2)0.7369 (2)0.91560 (18)0.0507 (5)
C60.1106 (3)0.7009 (2)0.99895 (19)0.0587 (5)
H60.07620.69461.08910.070*
C70.2793 (3)0.6715 (2)0.9538 (2)0.0600 (5)
C80.3471 (2)0.7286 (2)0.79945 (19)0.0553 (5)
C90.2154 (2)0.7232 (2)0.72078 (17)0.0491 (4)
C100.0498 (2)0.7378 (2)0.77398 (17)0.0488 (4)
C110.1470 (3)0.7475 (4)0.4749 (2)0.0851 (8)
H11B0.12950.84790.39850.128*
H11A0.25550.74050.52880.128*
H11C0.13610.66130.44150.128*
C120.4083 (3)0.9043 (3)0.7538 (3)0.0790 (7)
H12A0.45280.94530.65690.119*
H12B0.49220.91100.80260.119*
H12C0.31800.96620.77350.119*
C130.3426 (3)0.6738 (3)0.3381 (2)0.0823 (7)
H13B0.34780.65950.25260.123*
H13C0.37800.57960.40300.123*
H13A0.41320.76440.32370.123*
C140.1737 (2)0.7743 (2)0.9643 (2)0.0574 (5)
H140.24830.71550.93530.069*
C150.2245 (3)0.7260 (3)1.1202 (2)0.0831 (7)
H15A0.20590.61481.16440.125*
H15C0.33910.74341.14380.125*
H15B0.16020.78951.15010.125*
C160.1950 (3)0.9525 (3)0.8936 (3)0.0731 (6)
H16C0.12051.01290.91800.110*
H16A0.30620.97640.92240.110*
H16B0.17150.98040.79580.110*
H30.506 (4)0.574 (4)0.846 (3)0.116 (11)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.0766 (10)0.1039 (12)0.0479 (7)0.0129 (9)0.0140 (7)0.0365 (8)
O20.0990 (13)0.1237 (15)0.0674 (9)0.0631 (11)0.0479 (9)0.0525 (10)
O30.0641 (10)0.1039 (12)0.0623 (9)0.0395 (9)0.0222 (7)0.0353 (9)
C10.0544 (11)0.0652 (12)0.0471 (9)0.0130 (9)0.0102 (8)0.0209 (8)
C20.0646 (13)0.0645 (12)0.0406 (9)0.0096 (10)0.0127 (8)0.0191 (8)
C30.0590 (12)0.0712 (13)0.0483 (10)0.0047 (10)0.0171 (8)0.0218 (9)
C40.0492 (10)0.0690 (12)0.0531 (10)0.0082 (9)0.0114 (8)0.0252 (9)
C50.0593 (12)0.0463 (9)0.0488 (9)0.0058 (8)0.0095 (8)0.0208 (7)
C60.0729 (13)0.0645 (12)0.0456 (9)0.0192 (10)0.0167 (8)0.0267 (9)
C70.0737 (13)0.0652 (12)0.0564 (11)0.0285 (10)0.0302 (9)0.0328 (9)
C80.0525 (11)0.0648 (12)0.0559 (10)0.0179 (9)0.0197 (8)0.0270 (9)
C90.0517 (11)0.0524 (10)0.0455 (9)0.0112 (8)0.0149 (7)0.0186 (8)
C100.0522 (11)0.0507 (10)0.0462 (9)0.0083 (8)0.0131 (7)0.0197 (8)
C110.0675 (15)0.131 (2)0.0654 (13)0.0055 (15)0.0253 (11)0.0406 (14)
C120.0713 (15)0.0798 (16)0.0950 (17)0.0025 (12)0.0364 (13)0.0327 (13)
C130.0836 (17)0.111 (2)0.0601 (12)0.0176 (15)0.0069 (11)0.0448 (13)
C140.0516 (11)0.0654 (12)0.0612 (11)0.0013 (9)0.0058 (8)0.0328 (9)
C150.0754 (16)0.1040 (19)0.0696 (14)0.0020 (14)0.0076 (11)0.0425 (13)
C160.0605 (14)0.0741 (14)0.0950 (16)0.0190 (11)0.0206 (12)0.0412 (13)
Geometric parameters (Å, º) top
O1—C21.369 (2)C8—C121.537 (3)
O1—C131.421 (3)C9—C101.403 (2)
O2—C71.224 (2)C11—H11B0.9600
O3—C81.416 (2)C11—H11A0.9600
O3—H30.87 (3)C11—H11C0.9600
C1—C21.377 (3)C12—H12A0.9600
C1—C91.389 (2)C12—H12B0.9600
C1—H10.9300C12—H12C0.9600
C2—C31.401 (3)C13—H13B0.9600
C3—C41.388 (3)C13—H13C0.9600
C3—C111.502 (3)C13—H13A0.9600
C4—C101.399 (3)C14—C161.524 (3)
C4—H40.9300C14—C151.530 (3)
C5—C61.343 (3)C14—H140.9800
C5—C101.484 (2)C15—H15A0.9600
C5—C141.517 (3)C15—H15C0.9600
C6—C71.441 (3)C15—H15B0.9600
C6—H60.9300C16—H16C0.9600
C7—C81.526 (3)C16—H16A0.9600
C8—C91.510 (2)C16—H16B0.9600
C2—O1—C13118.06 (17)C3—C11—H11A109.5
C8—O3—H3109 (2)H11B—C11—H11A109.5
C2—C1—C9120.19 (18)C3—C11—H11C109.5
C2—C1—H1119.9H11B—C11—H11C109.5
C9—C1—H1119.9H11A—C11—H11C109.5
O1—C2—C1123.97 (18)C8—C12—H12A109.5
O1—C2—C3114.86 (17)C8—C12—H12B109.5
C1—C2—C3121.16 (17)H12A—C12—H12B109.5
C4—C3—C2117.66 (18)C8—C12—H12C109.5
C4—C3—C11121.55 (19)H12A—C12—H12C109.5
C2—C3—C11120.78 (18)H12B—C12—H12C109.5
C3—C4—C10122.77 (18)O1—C13—H13B109.5
C3—C4—H4118.6O1—C13—H13C109.5
C10—C4—H4118.6H13B—C13—H13C109.5
C6—C5—C10119.94 (17)O1—C13—H13A109.5
C6—C5—C14121.17 (16)H13B—C13—H13A109.5
C10—C5—C14118.89 (16)H13C—C13—H13A109.5
C5—C6—C7122.39 (17)C5—C14—C16109.12 (17)
C5—C6—H6118.8C5—C14—C15114.28 (18)
C7—C6—H6118.8C16—C14—C15109.79 (18)
O2—C7—C6123.11 (19)C5—C14—H14107.8
O2—C7—C8118.86 (19)C16—C14—H14107.8
C6—C7—C8117.93 (16)C15—C14—H14107.8
O3—C8—C9110.78 (15)C14—C15—H15A109.5
O3—C8—C7111.14 (15)C14—C15—H15C109.5
C9—C8—C7111.84 (17)H15A—C15—H15C109.5
O3—C8—C12108.56 (18)C14—C15—H15B109.5
C9—C8—C12107.82 (16)H15A—C15—H15B109.5
C7—C8—C12106.49 (17)H15C—C15—H15B109.5
C1—C9—C10120.60 (17)C14—C16—H16C109.5
C1—C9—C8119.16 (17)C14—C16—H16A109.5
C10—C9—C8120.17 (15)H16C—C16—H16A109.5
C4—C10—C9117.56 (16)C14—C16—H16B109.5
C4—C10—C5122.48 (17)H16C—C16—H16B109.5
C9—C10—C5119.89 (16)H16A—C16—H16B109.5
C3—C11—H11B109.5
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O3—H3···O2i0.87 (3)2.08 (3)2.892 (2)156.3
C13—H13B···O2ii0.962.513.467 (2)177
Symmetry codes: (i) x+1, y+1, z+2; (ii) x, y, z1.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O3—H3···O2i0.87 (3)2.08 (3)2.892 (2)156.3
C13—H13B···O2ii0.962.513.467 (2)177
Symmetry codes: (i) x+1, y+1, z+2; (ii) x, y, z1.
 

Acknowledgements

The authors thank the Academy of Sciences of the Republic of Uzbekistan for supporting this work (project Nos. F7–T048 and I5–FA–18897)

References

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First citationSuzuki, H., Yasuda, S. & Hanzawa, M. (1972). Mokuzai Gakkaishi, 18, 617–622.  CAS

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