Methyl 2,2-dimeth­oxy-8-oxo-1-oxaspiro­[4.5]deca-6,9-diene-3-carboxyl­ate

Lou, Y.

doi:10.1107/S1600536812011737

organic compounds

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ISSN: 2056-9890

Volume 68| Part 4| April 2012| Page o1152

doi:10.1107/S1600536812011737

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Methyl 2,2-dimethoxy-8-oxo-1-oxaspiro[4.5]deca-6,9-diene-3-carboxylate

Yongbing Lou ^a ^*

^aSchool of Chemistry and Chemical Engineering, Southeast University, Southeast University Road 2, Jiangning District, 211189 Nanjing, People's Republic of China
^*Correspondence e-mail: lou@seu.edu.cn

(Received 2 December 2011; accepted 18 March 2012; online 24 March 2012)

In the title molecule, C₁₃H₁₆O₆, the cyclohexa-1,4-diene ring adopts a flat boat conformation (r.m.s. deviation from planarity = 0.060 Å) and the five-membered tetrahydrofuran ring adopts an envelope conformation with the carboxyl group-substituted C atom as the flap. The dihedral angle at the spiro junction is 89.1 (1)°. In the crystal, molecules are linked through weak C—H⋯O and van der Waals interactions.

Related literature

For background to bioactive tetronic acid derivatives, see: Fischer et al. (1993 ); Bayer Aktiengesellschaft (1995).

Experimental

Crystal data

C₁₃H₁₆O₆
M_r = 268.26
Monoclinic, P 2₁ /c
a = 6.5324 (7) Å
b = 11.7519 (12) Å
c = 17.4204 (18) Å
β = 97.723 (2)°
V = 1325.2 (2) Å³
Z = 4
Mo Kα radiation
μ = 0.11 mm⁻¹
T = 298 K
0.31 × 0.26 × 0.21 mm

Data collection

Bruker SMART CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2000 ) T_min = 0.958, T_max = 0.978
7015 measured reflections
2588 independent reflections
2140 reflections with I > 2σ(I)
R_int = 0.020

Refinement

R[F² > 2σ(F²)] = 0.048
wR(F²) = 0.140
S = 1.05
2588 reflections
175 parameters
H-atom parameters constrained
Δρ_max = 0.29 e Å⁻³
Δρ_min = −0.22 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C13—H13A⋯O3ⁱ	0.96	2.60	3.269 (3)	127
Symmetry code: (i) $[-x+1, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT; 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/S1600536812011737/qk2030sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812011737/qk2030Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536812011737/qk2030Isup3.cml

checkCIF report

Comment top

The chemistry of tetronic acid (tetrahydrofuran-2,4-dione) compounds has received increasing attention in recent years due to their high biological activity as herbicides and insecticides (Fischer et al., 1993). The company Bayer AG has developed three tetronic acid pesticides, spirodiclofen, spiromesifen, and spirotetramat (Bayer Aktiengesellschaft, 1995), which are now in wide use in crop protection. As part of our studies in this area, we describe here the structure of the title compound (Scheme 1).

The title molecule (Fig. 1) contains one six-membered and one five-membered ring connected with a spiro-carbon C4. All bond lengths in this spiro system adopt normal values, e.g. the double bonds C2═C3, C5═C6, and C1═O1 with values of 1.320 (3) Å, 1.322 (3) Å, and 1.219 (2) Å, respectively. The cyclohexadienone unit is slightly bent to a flat boat conformation with atoms C2, C3, C5, C6 being practically coplanar and C1, C4, and O1 by 0.087 (3), 0.0163 (3), and 0.191 (5) Å, respectively, off from the plane of the former atoms. The five-membered tetrahydrofuran ring adopts an envelope conformation with C8 by 0.558 (3) Å out of the least-squares plane through O2, C4, C7, and C9 (their r.m.s. deviation from l.s. plane is 0.017 Å). In the crystal (Fig. 2), the molecules are linked through weak van der Waals and C-H···O interactions.

Related literature top

For background to bioactive tetronic acid derivatives, see: Fischer et al. (1993); Bayer Aktiengesellschaft (1995).

Experimental top

The starting material and all intermediates are known from literature and are obtained by standard procedures. The title compound was synthesized starting with 4-hydroxybenzaldehyde according to Fig. 3. using standard procedures for the intermediates 2 through 5. Then, to a solution of 5 (800 mg, 3.36 mmol) in MeOH (12 ml) was added a solution of PhI(OAc)₂ (1.6 g, 4.97 mmol) in CH₂Cl₂ (7 ml) at room temperature. The mixture was stirred for 30 min. The solvent was removed under reduced pressure and the residue was purified by silica gel column chromatography (EtOAc: PE = 1:3) to afford 6 (648.1 mg, 72% yield). ¹H NMR (400 MHz, CDCl₃) δ 2.28 (dd, J =9.2 Hz, 13.6 Hz, 1H), 2.72 (dd, J = 8.0 Hz, 13.6 Hz, 1H), 3.38 (s, 3H), 3.46 (s, 3H), 3.78 (s, 3H), 6.15–6.20 (m, 2H), 6.89–6.92 (m, 1H), 7.07–7.10 (m, 1H). ¹³C NMR (100 MHz, CDCl₃) δ 36.9, 48.4, 49.9, 51.1, 52.4, 75.8, 122.2, 127.6, 148.2, 149.2, 169.5, 185.0.

Structure description top

For background to bioactive tetronic acid derivatives, see: Fischer et al. (1993); Bayer Aktiengesellschaft (1995).

Computing details top

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT (Bruker, 2000); 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. Molecular structure of the title compound. Displacement ellipsoids were drawn at the 30% probability level.
	Fig. 2. Packing diagram of the structure viewed down the a-axis.
	Fig. 3. Synthetic route for the title compound.

Methyl 2,2-dimethoxy-8-oxo-1-oxaspiro[4.5]deca-6,9-diene-3-carboxylate top

Crystal data top

C₁₃H₁₆O₆	F(000) = 568
M_r = 268.26	D_x = 1.345 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 2543 reflections
a = 6.5324 (7) Å	θ = 5.9–49.9°
b = 11.7519 (12) Å	µ = 0.11 mm⁻¹
c = 17.4204 (18) Å	T = 298 K
β = 97.723 (2)°	Prismatic, colorless
V = 1325.2 (2) Å³	0.31 × 0.26 × 0.21 mm
Z = 4

Data collection top

Bruker SMART CCD diffractometer	2588 independent reflections
Radiation source: fine-focus sealed tube	2140 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.020
φ and ω scans	θ_max = 26.0°, θ_min = 2.1°
Absorption correction: multi-scan (SADABS; Bruker, 2000)	h = −7→8
T_min = 0.958, T_max = 0.978	k = −14→14
7015 measured reflections	l = −13→21

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)] = 0.048	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.140	H-atom parameters constrained
S = 1.05	w = 1/[σ²(F_o²) + (0.0751P)² + 0.297P] where P = (F_o² + 2F_c²)/3
2588 reflections	(Δ/σ)_max < 0.001
175 parameters	Δρ_max = 0.29 e Å⁻³
0 restraints	Δρ_min = −0.22 e Å⁻³

Crystal data top

C₁₃H₁₆O₆	V = 1325.2 (2) Å³
M_r = 268.26	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 6.5324 (7) Å	µ = 0.11 mm⁻¹
b = 11.7519 (12) Å	T = 298 K
c = 17.4204 (18) Å	0.31 × 0.26 × 0.21 mm
β = 97.723 (2)°

Data collection top

Bruker SMART CCD diffractometer	2588 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2000)	2140 reflections with I > 2σ(I)
T_min = 0.958, T_max = 0.978	R_int = 0.020
7015 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.048	0 restraints
wR(F²) = 0.140	H-atom parameters constrained
S = 1.05	Δρ_max = 0.29 e Å⁻³
2588 reflections	Δρ_min = −0.22 e Å⁻³
175 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	−0.2524 (3)	0.60788 (16)	−0.03288 (8)	0.0876 (5)
O2	0.0228 (2)	0.64745 (11)	0.26381 (7)	0.0560 (4)
O3	0.5107 (3)	0.39189 (16)	0.31643 (8)	0.0826 (5)
O4	0.34081 (19)	0.39820 (12)	0.41846 (7)	0.0571 (4)
O5	0.08806 (19)	0.62430 (12)	0.39416 (7)	0.0567 (4)
O6	0.35585 (19)	0.64129 (11)	0.32927 (7)	0.0546 (4)
C1	−0.1786 (3)	0.60713 (17)	0.03521 (11)	0.0601 (5)
C2	0.0197 (3)	0.66200 (19)	0.06170 (12)	0.0665 (6)
H2	0.0846	0.7040	0.0267	0.080*
C3	0.1080 (3)	0.65306 (19)	0.13416 (12)	0.0639 (6)
H3	0.2302	0.6927	0.1491	0.077*
C4	0.0216 (3)	0.58253 (16)	0.19334 (10)	0.0510 (4)
C5	−0.1957 (3)	0.54671 (16)	0.16723 (11)	0.0553 (5)
H5	−0.2722	0.5170	0.2039	0.066*
C6	−0.2852 (3)	0.55504 (17)	0.09477 (12)	0.0601 (5)
H6	−0.4186	0.5272	0.0815	0.072*
C7	0.1620 (3)	0.47845 (17)	0.21615 (10)	0.0584 (5)
H7A	0.1032	0.4096	0.1916	0.070*
H7B	0.2989	0.4899	0.2018	0.070*
C8	0.1695 (3)	0.47217 (14)	0.30329 (9)	0.0460 (4)
H8	0.0463	0.4327	0.3160	0.055*
C9	0.1579 (2)	0.59822 (14)	0.32513 (9)	0.0440 (4)
C10	0.3594 (3)	0.41569 (15)	0.34472 (10)	0.0490 (4)
C11	0.5178 (3)	0.35071 (19)	0.46569 (12)	0.0659 (6)
H11A	0.5372	0.2734	0.4503	0.099*
H11B	0.4961	0.3525	0.5191	0.099*
H11C	0.6383	0.3945	0.4592	0.099*
C12	−0.1168 (4)	0.5942 (3)	0.40212 (17)	0.0983 (10)
H12A	−0.2091	0.6268	0.3604	0.147*
H12B	−0.1506	0.6224	0.4506	0.147*
H12C	−0.1304	0.5129	0.4008	0.147*
C13	0.3702 (4)	0.76269 (19)	0.33775 (14)	0.0778 (7)
H13A	0.3063	0.7985	0.2911	0.117*
H13B	0.5130	0.7846	0.3475	0.117*
H13C	0.3011	0.7861	0.3804	0.117*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0973 (12)	0.1070 (13)	0.0497 (9)	−0.0063 (10)	−0.0219 (8)	0.0074 (8)
O2	0.0571 (7)	0.0555 (7)	0.0502 (7)	0.0126 (6)	−0.0116 (6)	−0.0035 (5)
O3	0.0771 (10)	0.1179 (14)	0.0537 (9)	0.0494 (10)	0.0115 (7)	0.0034 (8)
O4	0.0570 (8)	0.0695 (9)	0.0441 (7)	0.0098 (6)	0.0041 (6)	0.0112 (6)
O5	0.0510 (7)	0.0703 (8)	0.0485 (7)	0.0051 (6)	0.0056 (6)	−0.0117 (6)
O6	0.0456 (7)	0.0566 (8)	0.0596 (8)	−0.0074 (5)	−0.0004 (6)	0.0070 (6)
C1	0.0633 (12)	0.0596 (11)	0.0518 (11)	0.0056 (9)	−0.0125 (9)	0.0026 (9)
C2	0.0652 (12)	0.0766 (14)	0.0554 (11)	−0.0081 (10)	−0.0006 (9)	0.0161 (10)
C3	0.0510 (11)	0.0787 (14)	0.0582 (12)	−0.0127 (9)	−0.0067 (9)	0.0101 (10)
C4	0.0487 (10)	0.0578 (11)	0.0431 (9)	0.0014 (8)	−0.0061 (7)	0.0020 (7)
C5	0.0511 (10)	0.0576 (11)	0.0547 (11)	−0.0061 (8)	−0.0021 (8)	0.0050 (8)
C6	0.0509 (10)	0.0617 (11)	0.0622 (12)	−0.0066 (9)	−0.0130 (9)	0.0016 (9)
C7	0.0630 (11)	0.0667 (12)	0.0420 (9)	0.0149 (9)	−0.0059 (8)	−0.0057 (8)
C8	0.0452 (9)	0.0484 (10)	0.0430 (9)	0.0024 (7)	0.0012 (7)	−0.0013 (7)
C9	0.0387 (8)	0.0505 (9)	0.0413 (9)	0.0014 (7)	−0.0001 (7)	−0.0002 (7)
C10	0.0560 (10)	0.0491 (9)	0.0412 (9)	0.0090 (8)	0.0039 (8)	−0.0024 (7)
C11	0.0665 (13)	0.0759 (14)	0.0525 (11)	0.0154 (10)	−0.0029 (9)	0.0168 (10)
C12	0.0590 (14)	0.152 (3)	0.0895 (18)	−0.0069 (15)	0.0299 (13)	−0.0282 (17)
C13	0.0921 (16)	0.0582 (12)	0.0756 (14)	−0.0239 (11)	−0.0158 (12)	0.0146 (11)

Geometric parameters (Å, º) top

O1—C1	1.219 (2)	C5—C6	1.321 (3)
O2—C9	1.4148 (19)	C5—H5	0.9300
O2—C4	1.444 (2)	C6—H6	0.9300
O3—C10	1.195 (2)	C7—C8	1.514 (2)
O4—C10	1.323 (2)	C7—H7A	0.9700
O4—C11	1.439 (2)	C7—H7B	0.9700
O5—C9	1.377 (2)	C8—C10	1.503 (2)
O5—C12	1.409 (3)	C8—C9	1.534 (2)
O6—C9	1.381 (2)	C8—H8	0.9800
O6—C13	1.436 (3)	C11—H11A	0.9600
C1—C6	1.460 (3)	C11—H11B	0.9600
C1—C2	1.465 (3)	C11—H11C	0.9600
C2—C3	1.320 (3)	C12—H12A	0.9600
C2—H2	0.9300	C12—H12B	0.9600
C3—C4	1.492 (3)	C12—H12C	0.9600
C3—H3	0.9300	C13—H13A	0.9600
C4—C5	1.492 (2)	C13—H13B	0.9600
C4—C7	1.549 (3)	C13—H13C	0.9600

C9—O2—C4	110.94 (13)	C10—C8—C9	111.85 (14)
C10—O4—C11	116.36 (15)	C7—C8—C9	101.87 (14)
C9—O5—C12	117.44 (16)	C10—C8—H8	109.4
C9—O6—C13	114.67 (16)	C7—C8—H8	109.4
O1—C1—C6	122.06 (19)	C9—C8—H8	109.4
O1—C1—C2	121.4 (2)	O5—C9—O6	106.90 (13)
C6—C1—C2	116.54 (16)	O5—C9—O2	108.78 (13)
C3—C2—C1	121.39 (19)	O6—C9—O2	111.98 (14)
C3—C2—H2	119.3	O5—C9—C8	117.70 (15)
C1—C2—H2	119.3	O6—C9—C8	106.86 (14)
C2—C3—C4	123.21 (18)	O2—C9—C8	104.72 (13)
C2—C3—H3	118.4	O3—C10—O4	123.58 (16)
C4—C3—H3	118.4	O3—C10—C8	125.45 (16)
O2—C4—C5	107.74 (15)	O4—C10—C8	110.94 (15)
O2—C4—C3	109.54 (16)	O4—C11—H11A	109.5
C5—C4—C3	112.28 (15)	O4—C11—H11B	109.5
O2—C4—C7	105.29 (13)	H11A—C11—H11B	109.5
C5—C4—C7	111.23 (16)	O4—C11—H11C	109.5
C3—C4—C7	110.48 (16)	H11A—C11—H11C	109.5
C6—C5—C4	123.44 (19)	H11B—C11—H11C	109.5
C6—C5—H5	118.3	O5—C12—H12A	109.5
C4—C5—H5	118.3	O5—C12—H12B	109.5
C5—C6—C1	121.19 (18)	H12A—C12—H12B	109.5
C5—C6—H6	119.4	O5—C12—H12C	109.5
C1—C6—H6	119.4	H12A—C12—H12C	109.5
C8—C7—C4	103.53 (14)	H12B—C12—H12C	109.5
C8—C7—H7A	111.1	O6—C13—H13A	109.5
C4—C7—H7A	111.1	O6—C13—H13B	109.5
C8—C7—H7B	111.1	H13A—C13—H13B	109.5
C4—C7—H7B	111.1	O6—C13—H13C	109.5
H7A—C7—H7B	109.0	H13A—C13—H13C	109.5
C10—C8—C7	114.59 (15)	H13B—C13—H13C	109.5

O1—C1—C2—C3	−174.2 (2)	C12—O5—C9—O2	55.5 (2)
C6—C1—C2—C3	7.7 (3)	C12—O5—C9—C8	−63.3 (2)
C1—C2—C3—C4	3.4 (4)	C13—O6—C9—O5	−62.06 (19)
C9—O2—C4—C5	122.48 (15)	C13—O6—C9—O2	57.0 (2)
C9—O2—C4—C3	−115.12 (16)	C13—O6—C9—C8	171.10 (15)
C9—O2—C4—C7	3.68 (19)	C4—O2—C9—O5	−151.91 (14)
C2—C3—C4—O2	−133.2 (2)	C4—O2—C9—O6	90.16 (17)
C2—C3—C4—C5	−13.5 (3)	C4—O2—C9—C8	−25.26 (18)
C2—C3—C4—C7	111.3 (2)	C10—C8—C9—O5	−79.84 (19)
O2—C4—C5—C6	134.4 (2)	C7—C8—C9—O5	157.31 (15)
C3—C4—C5—C6	13.7 (3)	C10—C8—C9—O6	40.30 (19)
C7—C4—C5—C6	−110.7 (2)	C7—C8—C9—O6	−82.55 (16)
C4—C5—C6—C1	−3.7 (3)	C10—C8—C9—O2	159.24 (14)
O1—C1—C6—C5	174.4 (2)	C7—C8—C9—O2	36.39 (17)
C2—C1—C6—C5	−7.5 (3)	C11—O4—C10—O3	1.8 (3)
O2—C4—C7—C8	19.56 (19)	C11—O4—C10—C8	−176.39 (16)
C5—C4—C7—C8	−96.87 (18)	C7—C8—C10—O3	11.3 (3)
C3—C4—C7—C8	137.73 (16)	C9—C8—C10—O3	−104.0 (2)
C4—C7—C8—C10	−154.35 (15)	C7—C8—C10—O4	−170.64 (16)
C4—C7—C8—C9	−33.39 (18)	C9—C8—C10—O4	74.07 (19)
C12—O5—C9—O6	176.6 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C13—H13A···O3ⁱ	0.96	2.60	3.269 (3)	127

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

Experimental details

Crystal data
Chemical formula	C₁₃H₁₆O₆
M_r	268.26
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	298
a, b, c (Å)	6.5324 (7), 11.7519 (12), 17.4204 (18)
β (°)	97.723 (2)
V (Å³)	1325.2 (2)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.11
Crystal size (mm)	0.31 × 0.26 × 0.21

Data collection
Diffractometer	Bruker SMART CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2000)
T_min, T_max	0.958, 0.978
No. of measured, independent and observed [I > 2σ(I)] reflections	7015, 2588, 2140
R_int	0.020
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.048, 0.140, 1.05
No. of reflections	2588
No. of parameters	175
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.29, −0.22

Computer programs: SMART (Bruker, 2000), SAINT (Bruker, 2000), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C13—H13A···O3ⁱ	0.96	2.60	3.269 (3)	127

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

Acknowledgements

This project was sponsored by the National Science Foundation of Jiangsu Province (No. BK2009262) and the Scientific Research Foundation for Returned Overseas Chinese Scholars, State Education Ministry.

References

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