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Evolution of the major spiro­adduct obtained by cyclo­addition of C,N-diphenyl­nitrone with 3-methyl­enephthalide in Zn/3 M HCl media gives a rearrangement product. The reaction did not stop at the formation of an aminoalcohol but was followed by dehydration; the title compound, C22H19NO2, was obtained after hydrogenation. It exists in the diastereoisomer SS/RR form. The packing is stabilized by weak N—H...O and C—H...O hydrogen-bond inter­actions.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807050039/rk2049sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536807050039/rk2049Isup2.hkl
Contains datablock I

CCDC reference: 667368

Key indicators

  • Single-crystal X-ray study
  • T = 180 K
  • Mean [sigma](C-C) = 0.003 Å
  • R factor = 0.037
  • wR factor = 0.083
  • Data-to-parameter ratio = 12.6

checkCIF/PLATON results

No syntax errors found



Alert level B Crystal system given = triclinic PLAT029_ALERT_3_B _diffrn_measured_fraction_theta_full Low ....... 0.94
Alert level C REFLT03_ALERT_3_C Reflection count < 95% complete From the CIF: _diffrn_reflns_theta_max 25.94 From the CIF: _diffrn_reflns_theta_full 25.00 From the CIF: _reflns_number_total 3123 TEST2: Reflns within _diffrn_reflns_theta_max Count of symmetry unique reflns 3340 Completeness (_total/calc) 93.50% PLAT022_ALERT_3_C Ratio Unique / Expected Reflections too Low .... 0.94 PLAT420_ALERT_2_C D-H Without Acceptor N1 - H1A ... ?
Alert level G PLAT793_ALERT_1_G Check the Absolute Configuration of C1 = ... S PLAT793_ALERT_1_G Check the Absolute Configuration of C3 = ... S
0 ALERT level A = In general: serious problem 1 ALERT level B = Potentially serious problem 3 ALERT level C = Check and explain 2 ALERT level G = General alerts; check 2 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 1 ALERT type 2 Indicator that the structure model may be wrong or deficient 3 ALERT type 3 Indicator that the structure quality may be low 0 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check

Comment top

We previously reported that 1,3-dipolar cycloaddition of C,N-diphenylnitrone (1) to 3-methylenephtalide (2) produced a mixture of diastereoisomers (Roussel et al., 2003). The molecular structure of the major cycloadduct (3a) was confirmed by single-crystal X-ray diffraction (Daran et al., 2006) (Fig. 1).

In a previous paper (Laghrib et al., 2007), we described the evolution of isoxazolidines obtained by cycloaddition of C-tolyl-N-phenylnitrone with Tulipalin A in Zn / HCl media. The reduction of the nitrogen-oxygen bond of the heterocycle led to a functionalized γ-lactam. This reduction process has been successfully applied for the preparation of biologically active compounds (Goti et al., 1997; Padwa et al., 1981; Jung & Vu, 1996). We report here, on the evolution of major spiroadduct (3a) treated with Zn / 3M HCl. The reaction did not stop at the formation of aminoalcohol but was followed by dehydratation and hydrogenation to give (4) (Fig.2).

1H and 13C NMR studies of (4) did not provide much information on the structural behaviour of this product, therefore, we conducted single-crystal X-ray diffraction studies to get detailed information of the stereochemistry of (4).

The title compound (4) is built up from a phtalide fragment connected to a 2-N-phenyl-2-phenylethyl moiety (Fig. 2). The structural anlysis shows that compound (4) is the (SR/RS) diastereoisomer. The phtalide group is planar as expected with the largest deviation from the mean plane being 0.030 (2) Å at C41. It makes a dihedral angle of 51.37 (6)° with the N-phenyl group and 81.06 (6)° with the benzene ring. The benzene and the N-phenyl rings are nearly perpendicular with a dihedral angle of 80.01 (7)°. The occurrence of weak N–H···O and C–H···O hydrogen bonding interactions (see Table) help in stabilizing the packing.

Related literature top

For related structures, see: Daran et al. (2006); Laghrib et al. (2007). For related literature, see: Goti et al. (1997); Jung & Vu (1996); Padwa et al. (1981); Roussel et al. (2003).

Experimental top

Spiroadduct (3a) was synthesized by the procedure described in (Roussel et al., 2003). Synthesis of (4): to a solution of spiroheterocycle (3a) (0.64 mmol) in the minimum volume of acetone (3 ml) was added activated zinc dust (61.18 mmol). To the resulting suspension was slowly added 3M HCl (52.5 ml). The mixture was then stirred for 2 h at room temperature. The zinc was filtered off and rinsed with 3 M HCl and CHCl3. To this mixture, while vigorously stirring, solid K2CO3 was slowly added until pH = 7. After stirring for two additional hours, the organic layer was separated, dried with Na2SO4, filtered and concentrated to give the product as a solid, which was recrystallized from CH2Cl2.

Refinement top

All H atoms attached to C atoms and N atom were fixed geometrically and treated as riding with C–H = 0.95 Å (aromatic), 0.99 Å (methylene), 1.00 Å (methine) and N–H = 0.88 Å with Uiso(H) = 1.2Ueq(C or N).

Structure description top

We previously reported that 1,3-dipolar cycloaddition of C,N-diphenylnitrone (1) to 3-methylenephtalide (2) produced a mixture of diastereoisomers (Roussel et al., 2003). The molecular structure of the major cycloadduct (3a) was confirmed by single-crystal X-ray diffraction (Daran et al., 2006) (Fig. 1).

In a previous paper (Laghrib et al., 2007), we described the evolution of isoxazolidines obtained by cycloaddition of C-tolyl-N-phenylnitrone with Tulipalin A in Zn / HCl media. The reduction of the nitrogen-oxygen bond of the heterocycle led to a functionalized γ-lactam. This reduction process has been successfully applied for the preparation of biologically active compounds (Goti et al., 1997; Padwa et al., 1981; Jung & Vu, 1996). We report here, on the evolution of major spiroadduct (3a) treated with Zn / 3M HCl. The reaction did not stop at the formation of aminoalcohol but was followed by dehydratation and hydrogenation to give (4) (Fig.2).

1H and 13C NMR studies of (4) did not provide much information on the structural behaviour of this product, therefore, we conducted single-crystal X-ray diffraction studies to get detailed information of the stereochemistry of (4).

The title compound (4) is built up from a phtalide fragment connected to a 2-N-phenyl-2-phenylethyl moiety (Fig. 2). The structural anlysis shows that compound (4) is the (SR/RS) diastereoisomer. The phtalide group is planar as expected with the largest deviation from the mean plane being 0.030 (2) Å at C41. It makes a dihedral angle of 51.37 (6)° with the N-phenyl group and 81.06 (6)° with the benzene ring. The benzene and the N-phenyl rings are nearly perpendicular with a dihedral angle of 80.01 (7)°. The occurrence of weak N–H···O and C–H···O hydrogen bonding interactions (see Table) help in stabilizing the packing.

For related structures, see: Daran et al. (2006); Laghrib et al. (2007). For related literature, see: Goti et al. (1997); Jung & Vu (1996); Padwa et al. (1981); Roussel et al. (2003).

Computing details top

Data collection: IPDS (Stoe, 2000); cell refinement: IPDS (Stoe, 2000); data reduction: X-RED (Stoe, 1996); program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPIII (Burnett & Johnson, 1996) and ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures top
[Figure 1] Fig. 1. The scheme of formation the major cycloadduct (3a), which confirmed by single-crystal X-ray diffraction (Daran et al., 2006).
[Figure 2] Fig. 2. The scheme of formation the title compound (4).
[Figure 3] Fig. 3. Molecular view of the title compound with the atom-labelling scheme. Displacements ellipsoids are shown at the 50% probability level. H atoms are represented as small spheres of arbitrary radii.
(3SR,2'SR)-3-(2'-Anilino-2'-phenylethyl)phtalide top
Crystal data top
C22H19NO2Z = 2
Mr = 329.38F(000) = 348
Triclinic, P1Dx = 1.281 Mg m3
a = 6.303 (2) ÅMo Kα radiation, λ = 0.71073 Å
b = 7.774 (2) ÅCell parameters from 1428 reflections
c = 17.466 (5) Åθ = 2.2–26.2°
α = 88.15 (3)°µ = 0.08 mm1
β = 88.99 (4)°T = 180 K
γ = 86.62 (4)°Plate, colourless
V = 853.8 (4) Å30.28 × 0.14 × 0.06 mm
Data collection top
Stoe IPDS
diffractometer
1706 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.064
Graphite monochromatorθmax = 25.0°, θmin = 2.3°
φ scansh = 77
7801 measured reflectionsk = 99
2852 independent reflectionsl = 2020
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)] = 0.037Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.083H-atom parameters constrained
S = 0.81 w = 1/[σ2(Fo2) + (0.0408P)2
where P = (Fo2 + 2Fc2)/3
2852 reflections(Δ/σ)max = 0.001
226 parametersΔρmax = 0.16 e Å3
0 restraintsΔρmin = 0.16 e Å3
Crystal data top
C22H19NO2γ = 86.62 (4)°
Mr = 329.38V = 853.8 (4) Å3
Triclinic, P1Z = 2
a = 6.303 (2) ÅMo Kα radiation
b = 7.774 (2) ŵ = 0.08 mm1
c = 17.466 (5) ÅT = 180 K
α = 88.15 (3)°0.28 × 0.14 × 0.06 mm
β = 88.99 (4)°
Data collection top
Stoe IPDS
diffractometer
1706 reflections with I > 2σ(I)
7801 measured reflectionsRint = 0.064
2852 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0370 restraints
wR(F2) = 0.083H-atom parameters constrained
S = 0.81Δρmax = 0.16 e Å3
2852 reflectionsΔρmin = 0.16 e Å3
226 parameters
Special details top

Experimental. The data were collected on a Stoe Imaging Plate Diffraction System (IPDS). The crystal-to-detector distance was 70 mm. 167 frames (3 min per frame) were obtained with 0 < φ < 250.5° and with the crystals rotated through 1.5° in φ. Coverage of the unique set was over 93.5% complete to at least 26.08°. Crystal decay was monitored by measuring 200 reflections per frame. The Stoe IPDS because of the fixed phi spindle does not allow easy access to the cusp of data along the mount axis which explains why the _diffrn_measured_fraction_theta_full is low, 0.94. This is an instrumentation-based restriction, which the authors have little control over.

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 > 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
C10.6495 (3)0.8355 (2)0.27286 (9)0.0254 (4)
H10.53580.92300.25600.030*
C20.6137 (3)0.6640 (2)0.23486 (9)0.0272 (4)
H2A0.73790.58340.24560.033*
H2B0.48790.61400.25960.033*
C30.5806 (3)0.6733 (2)0.14912 (9)0.0247 (4)
H30.70250.72740.12230.030*
C40.2424 (3)0.6721 (3)0.09876 (9)0.0289 (5)
C310.5482 (3)0.4991 (2)0.11756 (9)0.0239 (4)
C410.3477 (3)0.5016 (2)0.08731 (9)0.0248 (4)
C510.2692 (3)0.3550 (3)0.05605 (9)0.0321 (5)
H510.13080.35730.03520.039*
C610.4010 (4)0.2075 (3)0.05679 (10)0.0387 (5)
H610.35340.10600.03540.046*
C710.6024 (4)0.2038 (3)0.08808 (10)0.0392 (5)
H710.68870.09940.08860.047*
C810.6799 (3)0.3501 (3)0.11865 (9)0.0322 (5)
H810.81810.34790.13950.039*
C1110.9257 (3)1.0536 (2)0.26694 (9)0.0241 (4)
C1121.1168 (3)1.1053 (2)0.23592 (9)0.0273 (4)
H1121.19211.03480.19990.033*
C1131.1997 (3)1.2580 (3)0.25650 (10)0.0310 (5)
H1131.33231.28980.23550.037*
C1141.0895 (3)1.3644 (2)0.30772 (10)0.0321 (5)
H1141.14581.46920.32200.039*
C1150.8979 (3)1.3164 (2)0.33753 (9)0.0303 (5)
H1150.82161.38930.37240.036*
C1160.8137 (3)1.1633 (2)0.31757 (9)0.0274 (4)
H1160.68011.13290.33830.033*
C1210.6298 (3)0.8057 (2)0.35941 (9)0.0265 (4)
C1220.8025 (3)0.7506 (2)0.40326 (9)0.0321 (5)
H1220.93990.73820.38020.039*
C1230.7758 (4)0.7132 (3)0.48085 (10)0.0406 (5)
H1230.89480.67330.51050.049*
C1240.5789 (4)0.7336 (3)0.51517 (11)0.0451 (6)
H1240.56150.70790.56840.054*
C1250.4071 (4)0.7910 (3)0.47233 (11)0.0486 (6)
H1250.27070.80590.49600.058*
C1260.4324 (3)0.8273 (3)0.39477 (10)0.0385 (5)
H1260.31280.86740.36550.046*
N10.8532 (2)0.8946 (2)0.24813 (8)0.0309 (4)
H1A0.93610.82660.21970.037*
O10.38175 (19)0.77239 (16)0.13285 (6)0.0298 (3)
O20.0643 (2)0.72846 (19)0.08469 (7)0.0448 (4)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0253 (10)0.0290 (11)0.0227 (9)0.0062 (9)0.0024 (7)0.0033 (8)
C20.0311 (11)0.0294 (11)0.0216 (8)0.0062 (9)0.0027 (7)0.0021 (8)
C30.0195 (10)0.0293 (11)0.0253 (9)0.0010 (9)0.0016 (7)0.0001 (8)
C40.0252 (11)0.0414 (13)0.0204 (9)0.0025 (10)0.0013 (8)0.0063 (8)
C310.0259 (10)0.0278 (11)0.0183 (8)0.0038 (9)0.0020 (7)0.0031 (7)
C410.0262 (10)0.0316 (11)0.0174 (8)0.0065 (9)0.0027 (7)0.0048 (8)
C510.0339 (11)0.0409 (13)0.0231 (9)0.0140 (11)0.0011 (8)0.0058 (9)
C610.0602 (15)0.0329 (13)0.0246 (10)0.0137 (12)0.0026 (9)0.0080 (9)
C710.0592 (15)0.0280 (12)0.0299 (10)0.0027 (11)0.0035 (10)0.0049 (9)
C810.0341 (12)0.0355 (12)0.0265 (10)0.0010 (10)0.0000 (8)0.0019 (8)
C1110.0251 (10)0.0264 (11)0.0209 (9)0.0028 (9)0.0030 (7)0.0003 (8)
C1120.0268 (11)0.0296 (11)0.0255 (9)0.0019 (9)0.0015 (8)0.0006 (8)
C1130.0272 (11)0.0326 (12)0.0332 (10)0.0053 (10)0.0012 (8)0.0037 (9)
C1140.0409 (13)0.0266 (11)0.0298 (10)0.0089 (10)0.0034 (9)0.0008 (8)
C1150.0387 (12)0.0277 (12)0.0246 (9)0.0012 (10)0.0003 (8)0.0033 (8)
C1160.0269 (11)0.0308 (11)0.0249 (9)0.0039 (9)0.0030 (7)0.0038 (8)
C1210.0311 (11)0.0263 (11)0.0230 (9)0.0064 (9)0.0006 (8)0.0064 (8)
C1220.0328 (12)0.0361 (12)0.0279 (10)0.0021 (10)0.0027 (8)0.0066 (9)
C1230.0480 (14)0.0443 (14)0.0295 (10)0.0001 (12)0.0105 (9)0.0018 (9)
C1240.0549 (15)0.0545 (15)0.0257 (10)0.0036 (13)0.0025 (10)0.0005 (10)
C1250.0404 (13)0.0701 (17)0.0346 (11)0.0037 (13)0.0123 (10)0.0017 (11)
C1260.0268 (11)0.0565 (15)0.0322 (11)0.0037 (11)0.0001 (8)0.0018 (10)
N10.0305 (9)0.0307 (10)0.0328 (8)0.0095 (8)0.0096 (7)0.0128 (7)
O10.0283 (7)0.0317 (8)0.0298 (7)0.0007 (6)0.0061 (5)0.0077 (6)
O20.0276 (8)0.0636 (11)0.0433 (8)0.0077 (8)0.0087 (6)0.0151 (7)
Geometric parameters (Å, º) top
C1—N11.443 (2)C111—N11.393 (2)
C1—C1211.526 (2)C111—C1161.401 (2)
C1—C21.539 (2)C112—C1131.385 (3)
C1—H11.0000C112—H1120.9500
C2—C31.514 (2)C113—C1141.388 (2)
C2—H2A0.9900C113—H1130.9500
C2—H2B0.9900C114—C1151.374 (3)
C3—O11.459 (2)C114—H1140.9500
C3—C311.505 (2)C115—C1161.389 (3)
C3—H31.0000C115—H1150.9500
C4—O21.207 (2)C116—H1160.9500
C4—O11.365 (2)C121—C1221.381 (3)
C4—C411.465 (3)C121—C1261.383 (3)
C31—C411.377 (2)C122—C1231.386 (3)
C31—C811.385 (3)C122—H1220.9500
C41—C511.399 (3)C123—C1241.372 (3)
C51—C611.376 (3)C123—H1230.9500
C51—H510.9500C124—C1251.371 (3)
C61—C711.389 (3)C124—H1240.9500
C61—H610.9500C125—C1261.383 (3)
C71—C811.389 (3)C125—H1250.9500
C71—H710.9500C126—H1260.9500
C81—H810.9500N1—H1A0.8800
C111—C1121.388 (3)
N1—C1—C121113.53 (14)C112—C111—C116118.24 (16)
N1—C1—C2109.13 (14)N1—C111—C116122.22 (16)
C121—C1—C2107.81 (16)C113—C112—C111121.20 (16)
N1—C1—H1108.8C113—C112—H112119.4
C121—C1—H1108.8C111—C112—H112119.4
C2—C1—H1108.8C112—C113—C114120.14 (18)
C3—C2—C1116.27 (15)C112—C113—H113119.9
C3—C2—H2A108.2C114—C113—H113119.9
C1—C2—H2A108.2C115—C114—C113119.20 (18)
C3—C2—H2B108.2C115—C114—H114120.4
C1—C2—H2B108.2C113—C114—H114120.4
H2A—C2—H2B107.4C114—C115—C116121.14 (17)
O1—C3—C31103.91 (14)C114—C115—H115119.4
O1—C3—C2109.13 (13)C116—C115—H115119.4
C31—C3—C2112.10 (15)C115—C116—C111120.04 (17)
O1—C3—H3110.5C115—C116—H116120.0
C31—C3—H3110.5C111—C116—H116120.0
C2—C3—H3110.5C122—C121—C126118.79 (17)
O2—C4—O1120.36 (17)C122—C121—C1121.80 (16)
O2—C4—C41131.13 (18)C126—C121—C1119.35 (16)
O1—C4—C41108.50 (15)C121—C122—C123120.20 (19)
C41—C31—C81121.00 (17)C121—C122—H122119.9
C41—C31—C3108.59 (15)C123—C122—H122119.9
C81—C31—C3130.33 (16)C124—C123—C122120.47 (19)
C31—C41—C51121.69 (18)C124—C123—H123119.8
C31—C41—C4108.45 (15)C122—C123—H123119.8
C51—C41—C4129.77 (17)C125—C124—C123119.72 (19)
C61—C51—C41117.12 (18)C125—C124—H124120.1
C61—C51—H51121.4C123—C124—H124120.1
C41—C51—H51121.4C124—C125—C126120.1 (2)
C51—C61—C71121.41 (18)C124—C125—H125120.0
C51—C61—H61119.3C126—C125—H125120.0
C71—C61—H61119.3C125—C126—C121120.71 (19)
C61—C71—C81121.17 (19)C125—C126—H126119.6
C61—C71—H71119.4C121—C126—H126119.6
C81—C71—H71119.4C111—N1—C1123.48 (14)
C31—C81—C71117.60 (18)C111—N1—H1A118.3
C31—C81—H81121.2C1—N1—H1A118.3
C71—C81—H81121.2C4—O1—C3110.49 (13)
C112—C111—N1119.53 (15)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1A···O2i0.882.603.390 (2)150
C3—H3···O2i1.002.363.279 (3)152
C51—H51···O2ii0.952.573.366 (2)141
Symmetry codes: (i) x+1, y, z; (ii) x, y+1, z.

Experimental details

Crystal data
Chemical formulaC22H19NO2
Mr329.38
Crystal system, space groupTriclinic, P1
Temperature (K)180
a, b, c (Å)6.303 (2), 7.774 (2), 17.466 (5)
α, β, γ (°)88.15 (3), 88.99 (4), 86.62 (4)
V3)853.8 (4)
Z2
Radiation typeMo Kα
µ (mm1)0.08
Crystal size (mm)0.28 × 0.14 × 0.06
Data collection
DiffractometerStoe IPDS
Absorption correction
No. of measured, independent and
observed [I > 2σ(I)] reflections
7801, 2852, 1706
Rint0.064
(sin θ/λ)max1)0.595
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.037, 0.083, 0.81
No. of reflections2852
No. of parameters226
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.16, 0.16

Computer programs: IPDS (Stoe, 2000), X-RED (Stoe, 1996), SIR97 (Altomare et al., 1999), SHELXL97 (Sheldrick, 1997), ORTEPIII (Burnett & Johnson, 1996) and ORTEP-3 for Windows (Farrugia, 1997), WinGX (Farrugia, 1999).

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1A···O2i0.882.603.390 (2)149.5
C3—H3···O2i1.002.363.279 (3)151.9
C51—H51···O2ii0.952.573.366 (2)141.1
Symmetry codes: (i) x+1, y, z; (ii) x, y+1, z.
 

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