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Two diastereoisomers of the title compound, C22H17NO3, have been prepared by [3 + 2]-cyclo­addition of 3-methyl­ene­phthalide with C,N-diphenyl­nitrone. The assigned structures of these compounds were supported by NMR data. The mol­ecular structure of the major cyclo­adduct was confirmed by single-crystal X-ray diffraction.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536805042169/su6261sup1.cif
Contains datablocks Spiro3, 3a

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536805042169/su62613asup2.hkl
Contains datablock 3a

CCDC reference: 296683

Key indicators

  • Single-crystal X-ray study
  • T = 180 K
  • Mean [sigma](C-C)= 0.002 Å
  • R factor = 0.048
  • wR factor = 0.127
  • Data-to-parameter ratio = 18.0

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Alert level A PUBL024_ALERT_1_A The number of authors is greater than 5. Please specify the role of each of the co-authors for your paper.
Author Response: The rather large number of authors (>5) is related to the fact that the work, owing to the shortage of equipment in Morocco, has been realized in collaboration between different groups: - Laboratoire des Substances Naturelles, Synth\`ese et Dynamique Mol\'eculaire and Laboratoire de Chimie Physique des Mat\'eriaux, Facult\'e des Sciences et Techniques d'Errachidia, Morocco, for the synthetic part. - Laboratoire de Chimie des Mat\'eriaux et Interfaces, UFR Sciences et Techniques, 16 Route de Gray, F-25030 Besan\,con cedex, France, for IR and NMR spectroscopy. - Laboratoire de Chimie de Coordination, UPR8241, 205 route de Narbonne, 31077 Toulouse cedex, France, for the X-ray analyses.


1 ALERT level A = Data missing that is essential or data in wrong format 0 ALERT level G = General alerts. Data that may be required is missing

Comment top

The 1,3-dipolar cycloaddition reactions between nitrones (1,3-dipoles) and alkenes (dipolarophiles) is an extremely powerful synthetic method for the synthesis of the isoxazolidine ring system (Tufariello, 1984; Confalone & Huie, 1988; Torssell, 1988; Carruthers, 1990; Grünanger & Vita-Finzi, 1991; Frederickson, 1997). Best regarded as a concerted but asynchronous [3 + 2] suprafacial process, the reaction enables the creation of up to two new carbon stereocenters in a single step. In such a case, the [3 + 2]-addition could provide two pairs of regioisomeric (i.e. resulting from different addition senses) and diastereoisomeric (i.e. resulting from the endo or the exo addition) products via four possible transition states, as depicted in the scheme below.

[scheme1]

As part of our research on bicyclic spirocompounds (Fihi et al., 1995), we previously reported that the 1,3-dipolar cycloaddition of aromatic nitrile oxides with 3-methylenephthalide, (1), produced 3'-arylspiro[isobensofuran-1(3H),5'(4'H)isoxazol]-3-ones, (3), which possess good herbicidal and plant growth regulant activities (Howe & Liu, 1981). Recently, we reported the [3 + 2]-cycloaddition of methylene-γ-butyrolactones with several nitrones (Roussel et al., 2003). The reaction is highly regioselective and leads to a mixture of two diastereoisomers, the ratios of which were evaluated by 1H NMR (performed on the crude reaction mixture). The structures of the spiroadducts, (3a) and (3b), were elucidated only by 1H and 13C NMR. Our structural proposition was based on comparision with the spectroscopic data of similar adducts for which the structures are already established (Roussel et al., 2003; Cacciarini et al., 2000).

To confirm unambigously the structure assignments of (3a) and (3b), and to establish the absolute stereochemistry of each spiroheterocycle, a single-crystal X-ray study was carried out on the major spirocompound, (3a). As shown in Fig. 1, the stereochemistry of (3a) follows from the endo CO approach, which favors the maximum of π electrons in the same space region. The molecule is built up from isobenzofuran-2-one and diphenyloxazoline groups linked by the spiro atom C1. The isobenzofuran fragment is planar, the largest deviation being −0.0295 (0) Å for atom O9, and the ketone atom, O81, lies in this plane. The oxazoline moiety has a half-chair conformation with atom O1 lying above the C1/C11/C12/N1 mean plane by 0.603 (2) Å. The isobenzofuran and oxazoline groups make a dihedral angle of 72.95 (4)°. The two phenyl rings, C111–C116 and C121–C126, attached to the oxazoline, are twisted with respect to the C1/C11/C12/N1 mean plane by 19.80 (9) and 80.21 (5)°, respectively. They are inclined to one another by 80.95 (4)°. The bond lengths and angles within the whole molecule are comparable to values found for related compounds (Cambridge Structural Database, Version 5.26; Allen, 2002).

Experimental top

3-Methylenephthalide, (1), and C,N-diphenylnitrone, (2), were synthesized according to the literature procedures (Liu & Uwe or Liu & Howe, 1983; Brüning et al., 1973). A solution of (2) (1.97 g, 10 mmol), (1) (1.46 g, 10 mmol) and hydroquinone (0.05 g) in ethylacetate (40 ml) was stirred and refluxed for 24 h under an atmosphere of nitrogen. The solvent was then evaporated under reduced pressure. The residue was crystallized in ethanol, leading to a mixture of diastereoisomers (3a) and (3b). They were separated and purified by chromatography on silica gel (eluant chloroform/hexane/ether 50:45:5). The spirocompounds (3a) and (3b) were finally recrystallized from ethanol.

Refinement top

All H atoms were placed in geometrically idealized positions and constrained to ride on their parent atoms with C—H distances equal to 0.95–1.00 Å and Uiso(H) = 1.2Ueq(C). Please check changes to text.

Computing details top

Data collection: CrysAlis CCD (Oxford Diffraction, 2003); cell refinement: CrysAlis RED (Oxford Diffraction, 2003); data reduction: CrysAlis RED; program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures top
[Figure 1] Fig. 1. The molecular structure of (3a), showing the atom-labelling scheme and displacement ellipsoids drawn at the 30% probability level.
(3a) top
Crystal data top
C22H17NO3F(000) = 720
Mr = 343.37Dx = 1.337 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 3224 reflections
a = 5.1476 (6) Åθ = 3.1–28.3°
b = 15.3139 (18) ŵ = 0.09 mm1
c = 21.653 (3) ÅT = 180 K
β = 91.365 (10)°Block, colorless
V = 1706.4 (4) Å30.51 × 0.37 × 0.35 mm
Z = 4
Data collection top
Oxford Diffraction XCALIBUR
diffractometer
4219 independent reflections
Radiation source: fine-focus sealed tube2777 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.067
ωϕ scansθmax = 28.3°, θmin = 3.1°
Absorption correction: multi-scan
(Blessing, 1995)
h = 66
Tmin = 0.932, Tmax = 0.967k = 2019
13897 measured reflectionsl = 2827
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.048Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.127H-atom parameters constrained
S = 0.93 w = 1/[σ2(Fo2) + (0.0717P)2]
where P = (Fo2 + 2Fc2)/3
4219 reflections(Δ/σ)max < 0.001
235 parametersΔρmax = 0.21 e Å3
0 restraintsΔρmin = 0.22 e Å3
Crystal data top
C22H17NO3V = 1706.4 (4) Å3
Mr = 343.37Z = 4
Monoclinic, P21/nMo Kα radiation
a = 5.1476 (6) ŵ = 0.09 mm1
b = 15.3139 (18) ÅT = 180 K
c = 21.653 (3) Å0.51 × 0.37 × 0.35 mm
β = 91.365 (10)°
Data collection top
Oxford Diffraction XCALIBUR
diffractometer
4219 independent reflections
Absorption correction: multi-scan
(Blessing, 1995)
2777 reflections with I > 2σ(I)
Tmin = 0.932, Tmax = 0.967Rint = 0.067
13897 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0480 restraints
wR(F2) = 0.127H-atom parameters constrained
S = 0.93Δρmax = 0.21 e Å3
4219 reflectionsΔρmin = 0.22 e Å3
235 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
xyzUiso*/Ueq
C10.1354 (3)0.26085 (9)0.07689 (6)0.0272 (3)
C20.0393 (3)0.30234 (9)0.13496 (6)0.0272 (3)
C30.1528 (3)0.36359 (10)0.14395 (7)0.0349 (4)
H30.24740.38840.11010.042*
C40.2027 (3)0.38754 (11)0.20446 (7)0.0383 (4)
H40.33430.42950.21190.046*
C50.0655 (3)0.35187 (11)0.25406 (7)0.0382 (4)
H50.10520.36920.29490.046*
C60.1272 (3)0.29168 (11)0.24486 (6)0.0364 (4)
H60.22430.26770.27860.044*
C70.1752 (3)0.26721 (9)0.18465 (6)0.0291 (3)
C80.3625 (3)0.20312 (10)0.16154 (7)0.0347 (3)
C110.0587 (3)0.21464 (11)0.03401 (6)0.0342 (3)
H11A0.23540.23900.03850.041*
H11B0.06330.15120.04280.041*
C120.0429 (3)0.23208 (9)0.03141 (6)0.0275 (3)
H120.07930.27180.05440.033*
C1110.3874 (3)0.33815 (9)0.06237 (6)0.0273 (3)
C1120.5636 (3)0.40230 (10)0.04347 (7)0.0342 (3)
H1120.60230.41040.00070.041*
C1130.6825 (3)0.45418 (10)0.08675 (8)0.0414 (4)
H1130.80280.49770.07350.050*
C1140.6279 (3)0.44331 (11)0.14907 (8)0.0457 (4)
H1140.71470.47760.17870.055*
C1150.4469 (4)0.38237 (12)0.16760 (7)0.0472 (4)
H1150.40380.37630.21030.057*
C1160.3259 (3)0.32945 (10)0.12489 (7)0.0376 (4)
H1160.20140.28740.13840.045*
C1210.0813 (3)0.14899 (9)0.06793 (6)0.0257 (3)
C1220.1008 (3)0.12601 (10)0.11306 (6)0.0307 (3)
H1220.24180.16420.12240.037*
C1230.0796 (3)0.04775 (10)0.14489 (7)0.0373 (4)
H1230.20590.03260.17580.045*
C1240.1243 (3)0.00802 (10)0.13176 (7)0.0379 (4)
H1240.13870.06170.15340.045*
C1250.3073 (3)0.01452 (10)0.08701 (7)0.0393 (4)
H1250.44920.02350.07830.047*
C1260.2859 (3)0.09213 (10)0.05472 (7)0.0337 (3)
H1260.41120.10660.02350.040*
N10.2925 (2)0.27746 (8)0.01877 (5)0.0270 (3)
O10.25479 (18)0.32378 (6)0.04003 (4)0.0299 (2)
O90.33314 (19)0.19889 (7)0.09869 (4)0.0326 (3)
O810.5164 (2)0.15885 (9)0.18940 (5)0.0554 (4)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0276 (7)0.0275 (7)0.0266 (7)0.0022 (6)0.0034 (5)0.0012 (5)
C20.0277 (7)0.0282 (8)0.0259 (7)0.0019 (6)0.0019 (5)0.0017 (6)
C30.0349 (8)0.0383 (9)0.0314 (8)0.0068 (7)0.0011 (6)0.0021 (6)
C40.0368 (8)0.0393 (9)0.0391 (9)0.0092 (7)0.0049 (7)0.0057 (7)
C50.0397 (8)0.0461 (10)0.0290 (8)0.0018 (7)0.0035 (6)0.0087 (7)
C60.0394 (8)0.0441 (9)0.0257 (7)0.0044 (7)0.0019 (6)0.0022 (6)
C70.0302 (7)0.0302 (8)0.0268 (7)0.0007 (6)0.0009 (6)0.0011 (6)
C80.0367 (8)0.0357 (9)0.0317 (8)0.0053 (7)0.0010 (6)0.0006 (6)
C110.0315 (8)0.0434 (9)0.0280 (8)0.0067 (7)0.0037 (6)0.0040 (6)
C120.0258 (7)0.0314 (8)0.0252 (7)0.0025 (6)0.0004 (5)0.0004 (6)
C1110.0308 (7)0.0233 (7)0.0281 (7)0.0053 (6)0.0058 (6)0.0024 (5)
C1120.0374 (8)0.0294 (8)0.0359 (8)0.0001 (6)0.0033 (6)0.0037 (6)
C1130.0435 (9)0.0293 (8)0.0517 (10)0.0002 (7)0.0082 (7)0.0087 (7)
C1140.0568 (11)0.0339 (9)0.0471 (10)0.0035 (8)0.0177 (8)0.0139 (7)
C1150.0705 (12)0.0411 (10)0.0305 (8)0.0032 (9)0.0081 (8)0.0070 (7)
C1160.0510 (9)0.0330 (9)0.0288 (8)0.0015 (7)0.0019 (7)0.0028 (6)
C1210.0282 (7)0.0251 (7)0.0240 (7)0.0014 (6)0.0035 (5)0.0031 (5)
C1220.0313 (7)0.0319 (8)0.0288 (7)0.0043 (6)0.0010 (6)0.0005 (6)
C1230.0398 (9)0.0365 (9)0.0356 (8)0.0021 (7)0.0001 (7)0.0060 (7)
C1240.0455 (9)0.0251 (8)0.0437 (9)0.0014 (7)0.0127 (7)0.0016 (6)
C1250.0394 (8)0.0286 (8)0.0499 (9)0.0094 (7)0.0054 (7)0.0046 (7)
C1260.0321 (8)0.0317 (8)0.0371 (8)0.0035 (6)0.0035 (6)0.0039 (6)
N10.0320 (6)0.0287 (6)0.0203 (6)0.0020 (5)0.0033 (5)0.0028 (5)
O10.0373 (5)0.0295 (6)0.0230 (5)0.0033 (4)0.0054 (4)0.0034 (4)
O90.0358 (6)0.0342 (6)0.0279 (5)0.0073 (5)0.0038 (4)0.0015 (4)
O810.0616 (8)0.0626 (9)0.0418 (7)0.0327 (7)0.0047 (6)0.0033 (6)
Geometric parameters (Å, º) top
C1—O11.4026 (16)C111—C1121.392 (2)
C1—O91.4617 (16)C111—N11.4195 (17)
C1—C21.5030 (18)C112—C1131.382 (2)
C1—C111.5222 (19)C112—H1120.9500
C2—C71.3787 (19)C113—C1141.382 (2)
C2—C31.380 (2)C113—H1130.9500
C3—C41.391 (2)C114—C1151.372 (2)
C3—H30.9500C114—H1140.9500
C4—C51.384 (2)C115—C1161.388 (2)
C4—H40.9500C115—H1150.9500
C5—C61.372 (2)C116—H1160.9500
C5—H50.9500C121—C1221.3835 (19)
C6—C71.3844 (19)C121—C1261.3908 (19)
C6—H60.9500C122—C1231.388 (2)
C7—C81.472 (2)C122—H1220.9500
C8—O811.1951 (18)C123—C1241.378 (2)
C8—O91.3671 (17)C123—H1230.9500
C11—C121.5450 (18)C124—C1251.379 (2)
C11—H11A0.9900C124—H1240.9500
C11—H11B0.9900C125—C1261.385 (2)
C12—N11.4805 (17)C125—H1250.9500
C12—C1211.5134 (19)C126—H1260.9500
C12—H121.0000N1—O11.4743 (13)
C111—C1161.3892 (19)
O1—C1—O9108.57 (10)C116—C111—N1120.76 (13)
O1—C1—C2110.07 (11)C112—C111—N1119.91 (12)
O9—C1—C2104.17 (10)C113—C112—C111120.14 (14)
O1—C1—C11105.21 (11)C113—C112—H112119.9
O9—C1—C11109.71 (12)C111—C112—H112119.9
C2—C1—C11118.86 (11)C114—C113—C112120.65 (16)
C7—C2—C3120.48 (13)C114—C113—H113119.7
C7—C2—C1108.48 (12)C112—C113—H113119.7
C3—C2—C1131.03 (13)C115—C114—C113119.23 (15)
C2—C3—C4117.46 (14)C115—C114—H114120.4
C2—C3—H3121.3C113—C114—H114120.4
C4—C3—H3121.3C114—C115—C116120.97 (15)
C5—C4—C3121.67 (14)C114—C115—H115119.5
C5—C4—H4119.2C116—C115—H115119.5
C3—C4—H4119.2C115—C116—C111119.86 (15)
C6—C5—C4120.65 (14)C115—C116—H116120.1
C6—C5—H5119.7C111—C116—H116120.1
C4—C5—H5119.7C122—C121—C126118.88 (13)
C5—C6—C7117.68 (13)C122—C121—C12119.23 (12)
C5—C6—H6121.2C126—C121—C12121.77 (12)
C7—C6—H6121.2C121—C122—C123120.69 (13)
C2—C7—C6122.05 (13)C121—C122—H122119.7
C2—C7—C8108.61 (12)C123—C122—H122119.7
C6—C7—C8129.34 (13)C124—C123—C122120.08 (14)
O81—C8—O9122.13 (14)C124—C123—H123120.0
O81—C8—C7129.66 (14)C122—C123—H123120.0
O9—C8—C7108.20 (12)C123—C124—C125119.61 (14)
C1—C11—C12104.32 (11)C123—C124—H124120.2
C1—C11—H11A110.9C125—C124—H124120.2
C12—C11—H11A110.9C124—C125—C126120.56 (14)
C1—C11—H11B110.9C124—C125—H125119.7
C12—C11—H11B110.9C126—C125—H125119.7
H11A—C11—H11B108.9C125—C126—C121120.17 (14)
N1—C12—C121111.58 (11)C125—C126—H126119.9
N1—C12—C11102.89 (10)C121—C126—H126119.9
C121—C12—C11112.64 (12)C111—N1—O1108.28 (10)
N1—C12—H12109.8C111—N1—C12119.67 (11)
C121—C12—H12109.8O1—N1—C12104.71 (9)
C11—C12—H12109.8C1—O1—N1103.26 (9)
C116—C111—C112119.05 (13)C8—O9—C1110.50 (10)

Experimental details

Crystal data
Chemical formulaC22H17NO3
Mr343.37
Crystal system, space groupMonoclinic, P21/n
Temperature (K)180
a, b, c (Å)5.1476 (6), 15.3139 (18), 21.653 (3)
β (°) 91.365 (10)
V3)1706.4 (4)
Z4
Radiation typeMo Kα
µ (mm1)0.09
Crystal size (mm)0.51 × 0.37 × 0.35
Data collection
DiffractometerOxford Diffraction XCALIBUR
diffractometer
Absorption correctionMulti-scan
(Blessing, 1995)
Tmin, Tmax0.932, 0.967
No. of measured, independent and
observed [I > 2σ(I)] reflections
13897, 4219, 2777
Rint0.067
(sin θ/λ)max1)0.666
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.048, 0.127, 0.93
No. of reflections4219
No. of parameters235
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.21, 0.22

Computer programs: CrysAlis CCD (Oxford Diffraction, 2003), CrysAlis RED (Oxford Diffraction, 2003), CrysAlis RED, SIR97 (Altomare et al., 1999), SHELXL97 (Sheldrick, 1997), ORTEP-3 for Windows (Farrugia, 1997), WinGX (Farrugia, 1999).

 

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