organic compounds
Methyl 2-(1,3-dioxoisoindolin-2-yl)acrylate
aState Key Laboratory of Applied Organic Chemstry, College of Chemistry & Chemical Engineering, Lanzhou University, Lanzhou 730000, People's Republic of China
*Correspondence e-mail: pengyu@lzu.edu.cn
In the title compound, C12H9NO4, an important dehydroamino acid, the acrylate C=C double bond is not parallel to the adjacent carbonyl group and an s-trans configuration is also observed.
Related literature
For related literature, see: Cativiela et al. (2000); Clausen et al. (2002); Schmidt et al. (1988); Trost & Dake, (1997); Wirth (1997); Osborn et al. (1966). For related structures, see: Ajò et al. (1984; 1979); Busetti et al. (1984; 1986).
Experimental
Crystal data
|
Data collection: SMART (Bruker, 2000); cell SAINT (Bruker, 2000); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 2000); software used to prepare material for publication: SHELXTL.
Supporting information
https://doi.org/10.1107/S160053680706093X/hg2354sup1.cif
contains datablocks global, I. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S160053680706093X/hg2354Isup2.hkl
To a solution of phthalimide (740 mg, 5 mmol), triphenylphosphine (130 mg, 0.5 mmol) and sodium acetate (210 mg, 2.5 mmol) in 10 ml of toluene at 378 K were added sequentially acetic acid (0.14 ml, 2.5 mmol) and methyl propiolate (420 mg, 5 mmol). After 18 h, the reaction mixture was cooled and directly subjected to δ = 7.94–7.90 (m, 2H), 7.83–7.77 (m, 2H), 6.69 (s, 1H), 6.01 (s, 1H), 3.82 (s, 3H) p.p.m.; 13C NMR (50 MHz, CDCl3): δ = 166.2, 162.6, 134.2 (2 C), 131.7, 129.0, 127.9 (2 C), 123.8 (2 C), 52.7 p.p.m.. Single crystals suitable for X-ray determination were obtained by slow evaporation of a EtOAc solution over a period of several days.
on silica gel (Hexane: EtOAc = 2: 1) to yield 928 mg (80% yield) of the title compound. 1H NMR (200 MHz, CDCl3):All H atoms were placed geometrically (C—H values were set to 0.96 and 0.93 Å for atoms CH3, CH2, and CH (phenyl), respectively) and refined with a riding model, with Uiso(H) = 1.2 or 1.5 times Ueq(C).
Optical active nonproteinogenic amino acids (Clausen et al., 2002) are valuable compounds of high interest not only due to their remarkable pharmacological and biological activities but also for their role as a topographic probe for investigation of bioactive conformations of
and the mechanisms of enzyme reactions. Consequently, efficient and convenient methods for the preparation of optically pure enantiomers of amino acids are be general interest (Cativiela & Diaz-de-Villegas, 2000; Wirth, 1997). It is noteworthy that extraordinary progress has been made in the asymmetric hydrogenation of dehydroamino acids (Osborn et al., 1966; Schmidt et al., 1988), which serve as important precursors of saturated ones.The title compound belong to one of dehydroamino acids mentioned above. Its molecular structure is shown in Fig.1 and can be prepared conveniently through nucleophilic addition of phthalimide to propiolate according to the precedent procedure (Trost & Dake, 1997). The exceptionally large difference (Δ δ= 0.68 p.p.m.) between the chemical shifts of the two protons (Ha and Hb) on the double bond suggest that the chemical environments (e.g., deshielding effect of the phthalimidyl group) of them are considerably different. As shown in Fig. 1, An s-trans conformation is observed, which was discussed in detail other groups previously (Ajò et al., 1984; Ajò et al., 1979; Busetti, et al., 1984; Busetti, et al., 1986). The double bond (C9–C12) is not parallel with the carbonyl (C10–O1) group with the C12-C9_C10-O1 torsion angle -142.3 (2)° while the double bond (C9–C12) lies out of the plane of the phthalimidyl group with the torsion angle C7—N1—C9—C12 44.7 (3)°.
For related literature, see: Cativiela et al. (2000); Clausen et al. (2002); Schmidt et al. (1988); Trost & Dake, (1997); Wirth (1997); Osborn et al. (1966). For related structures, see: Ajò et al. (1984; 1979); Busetti et al. (1984; 1986).
Data collection: SMART (Bruker, 2000); cell
SMART (Bruker, 2000); data reduction: SAINT (Bruker, 2000); program(s) used to solve structure: SHELXL97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 2000); software used to prepare material for publication: SHELXTL (Bruker, 2000).Fig. 1. The independent components of (I), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level. |
C12H9NO4 | Z = 2 |
Mr = 231.20 | F(000) = 240 |
Triclinic, P1 | Dx = 1.415 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 6.5179 (3) Å | Cell parameters from 1079 reflections |
b = 7.4817 (4) Å | θ = 2.8–23.7° |
c = 11.7322 (6) Å | µ = 0.11 mm−1 |
α = 80.954 (2)° | T = 294 K |
β = 78.866 (2)° | Block, colorless |
γ = 76.723 (2)° | 0.20 × 0.18 × 0.15 mm |
V = 542.52 (5) Å3 |
Bruker APEX CCD area-detector diffractometer | 1984 independent reflections |
Radiation source: fine-focus sealed tube | 1497 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.016 |
phi and ω scans | θmax = 25.5°, θmin = 1.8° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −6→7 |
Tmin = 0.979, Tmax = 0.984 | k = −9→8 |
2932 measured reflections | l = −14→14 |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.041 | H-atom parameters constrained |
wR(F2) = 0.114 | w = 1/[σ2(Fo2) + (0.0506P)2 + 0.1136P] where P = (Fo2 + 2Fc2)/3 |
S = 1.04 | (Δ/σ)max < 0.001 |
1984 reflections | Δρmax = 0.18 e Å−3 |
156 parameters | Δρmin = −0.14 e Å−3 |
0 restraints | Extinction correction: SHELXL, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.044 (7) |
C12H9NO4 | γ = 76.723 (2)° |
Mr = 231.20 | V = 542.52 (5) Å3 |
Triclinic, P1 | Z = 2 |
a = 6.5179 (3) Å | Mo Kα radiation |
b = 7.4817 (4) Å | µ = 0.11 mm−1 |
c = 11.7322 (6) Å | T = 294 K |
α = 80.954 (2)° | 0.20 × 0.18 × 0.15 mm |
β = 78.866 (2)° |
Bruker APEX CCD area-detector diffractometer | 1984 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 1497 reflections with I > 2σ(I) |
Tmin = 0.979, Tmax = 0.984 | Rint = 0.016 |
2932 measured reflections |
R[F2 > 2σ(F2)] = 0.041 | 0 restraints |
wR(F2) = 0.114 | H-atom parameters constrained |
S = 1.04 | Δρmax = 0.18 e Å−3 |
1984 reflections | Δρmin = −0.14 e Å−3 |
156 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
C5 | 0.3823 (3) | 0.8001 (2) | 0.03710 (15) | 0.0475 (4) | |
C6 | 0.5949 (3) | 0.7126 (2) | 0.02643 (15) | 0.0471 (4) | |
C1 | 0.7069 (3) | 0.6511 (3) | −0.07723 (18) | 0.0594 (5) | |
H1 | 0.8502 | 0.5927 | −0.0841 | 0.071* | |
C2 | 0.5971 (4) | 0.6799 (3) | −0.17070 (18) | 0.0667 (6) | |
H2 | 0.6677 | 0.6396 | −0.2418 | 0.080* | |
C4 | 0.2737 (3) | 0.8285 (3) | −0.05580 (18) | 0.0618 (5) | |
H4 | 0.1303 | 0.8869 | −0.0489 | 0.074* | |
C3 | 0.3854 (4) | 0.7671 (3) | −0.15998 (18) | 0.0673 (6) | |
H3 | 0.3157 | 0.7852 | −0.2242 | 0.081* | |
C7 | 0.6660 (3) | 0.6964 (3) | 0.14049 (16) | 0.0503 (5) | |
C8 | 0.3091 (3) | 0.8473 (2) | 0.15854 (16) | 0.0485 (4) | |
N1 | 0.4864 (2) | 0.7786 (2) | 0.21650 (12) | 0.0483 (4) | |
C9 | 0.4784 (3) | 0.7876 (3) | 0.33739 (16) | 0.0512 (5) | |
C10 | 0.2984 (3) | 0.7159 (3) | 0.41433 (16) | 0.0560 (5) | |
C11 | 0.0631 (4) | 0.7296 (4) | 0.59378 (18) | 0.0740 (7) | |
H11A | −0.0473 | 0.7213 | 0.5525 | 0.111* | |
H11B | 0.0054 | 0.8140 | 0.6513 | 0.111* | |
H11C | 0.1182 | 0.6097 | 0.6318 | 0.111* | |
O2 | 0.2339 (2) | 0.7960 (2) | 0.51181 (11) | 0.0633 (4) | |
O1 | 0.2230 (3) | 0.5971 (3) | 0.39155 (13) | 0.0908 (6) | |
O4 | 0.1388 (2) | 0.9302 (2) | 0.20287 (13) | 0.0667 (4) | |
O3 | 0.8377 (2) | 0.6270 (2) | 0.16799 (13) | 0.0735 (5) | |
C12 | 0.6314 (3) | 0.8332 (3) | 0.3783 (2) | 0.0702 (6) | |
H12A | 0.7511 | 0.8612 | 0.3274 | 0.084* | |
H12B | 0.6198 | 0.8374 | 0.4582 | 0.084* |
U11 | U22 | U33 | U12 | U13 | U23 | |
C5 | 0.0503 (10) | 0.0393 (9) | 0.0514 (10) | −0.0052 (8) | −0.0077 (8) | −0.0076 (8) |
C6 | 0.0462 (10) | 0.0416 (10) | 0.0507 (10) | −0.0090 (8) | −0.0008 (8) | −0.0063 (8) |
C1 | 0.0592 (12) | 0.0547 (12) | 0.0595 (12) | −0.0115 (9) | 0.0063 (10) | −0.0126 (9) |
C2 | 0.0907 (17) | 0.0596 (13) | 0.0482 (12) | −0.0221 (12) | 0.0054 (11) | −0.0126 (9) |
C4 | 0.0660 (13) | 0.0545 (12) | 0.0644 (13) | −0.0011 (10) | −0.0197 (10) | −0.0114 (10) |
C3 | 0.0923 (17) | 0.0585 (13) | 0.0547 (12) | −0.0146 (12) | −0.0202 (11) | −0.0083 (10) |
C7 | 0.0414 (10) | 0.0476 (10) | 0.0584 (11) | −0.0055 (8) | −0.0031 (8) | −0.0081 (8) |
C8 | 0.0426 (10) | 0.0459 (10) | 0.0554 (11) | −0.0051 (8) | −0.0056 (8) | −0.0103 (8) |
N1 | 0.0416 (8) | 0.0536 (9) | 0.0472 (9) | −0.0035 (7) | −0.0052 (7) | −0.0102 (7) |
C9 | 0.0530 (11) | 0.0514 (11) | 0.0500 (11) | −0.0085 (8) | −0.0091 (8) | −0.0102 (8) |
C10 | 0.0640 (12) | 0.0582 (12) | 0.0486 (11) | −0.0144 (10) | −0.0094 (9) | −0.0116 (9) |
C11 | 0.0720 (14) | 0.1010 (19) | 0.0505 (12) | −0.0271 (13) | 0.0016 (10) | −0.0143 (11) |
O2 | 0.0649 (9) | 0.0775 (10) | 0.0517 (8) | −0.0216 (7) | −0.0003 (6) | −0.0216 (7) |
O1 | 0.1201 (14) | 0.1023 (13) | 0.0672 (10) | −0.0674 (12) | 0.0164 (9) | −0.0346 (9) |
O4 | 0.0460 (8) | 0.0774 (10) | 0.0729 (9) | 0.0052 (7) | −0.0061 (7) | −0.0287 (7) |
O3 | 0.0454 (8) | 0.0910 (11) | 0.0790 (10) | 0.0080 (7) | −0.0149 (7) | −0.0214 (8) |
C12 | 0.0627 (13) | 0.0895 (17) | 0.0636 (13) | −0.0207 (12) | −0.0133 (10) | −0.0135 (11) |
C5—C4 | 1.375 (3) | C8—O4 | 1.204 (2) |
C5—C6 | 1.381 (2) | C8—N1 | 1.408 (2) |
C5—C8 | 1.483 (3) | N1—C9 | 1.421 (2) |
C6—C1 | 1.379 (3) | C9—C12 | 1.317 (3) |
C6—C7 | 1.477 (3) | C9—C10 | 1.485 (3) |
C1—C2 | 1.385 (3) | C10—O1 | 1.196 (2) |
C1—H1 | 0.9300 | C10—O2 | 1.326 (2) |
C2—C3 | 1.375 (3) | C11—O2 | 1.449 (2) |
C2—H2 | 0.9300 | C11—H11A | 0.9600 |
C4—C3 | 1.384 (3) | C11—H11B | 0.9600 |
C4—H4 | 0.9300 | C11—H11C | 0.9600 |
C3—H3 | 0.9300 | C12—H12A | 0.9300 |
C7—O3 | 1.203 (2) | C12—H12B | 0.9300 |
C7—N1 | 1.408 (2) | ||
C4—C5—C6 | 120.94 (17) | O4—C8—C5 | 129.91 (17) |
C4—C5—C8 | 130.64 (17) | N1—C8—C5 | 105.68 (14) |
C6—C5—C8 | 108.42 (15) | C8—N1—C7 | 111.36 (15) |
C1—C6—C5 | 121.66 (18) | C8—N1—C9 | 123.22 (15) |
C1—C6—C7 | 129.53 (17) | C7—N1—C9 | 125.39 (15) |
C5—C6—C7 | 108.79 (15) | C12—C9—N1 | 122.78 (18) |
C6—C1—C2 | 117.30 (19) | C12—C9—C10 | 122.85 (18) |
C6—C1—H1 | 121.3 | N1—C9—C10 | 113.85 (15) |
C2—C1—H1 | 121.3 | O1—C10—O2 | 123.94 (19) |
C3—C2—C1 | 120.99 (19) | O1—C10—C9 | 123.63 (18) |
C3—C2—H2 | 119.5 | O2—C10—C9 | 112.41 (16) |
C1—C2—H2 | 119.5 | O2—C11—H11A | 109.5 |
C5—C4—C3 | 117.59 (19) | O2—C11—H11B | 109.5 |
C5—C4—H4 | 121.2 | H11A—C11—H11B | 109.5 |
C3—C4—H4 | 121.2 | O2—C11—H11C | 109.5 |
C2—C3—C4 | 121.5 (2) | H11A—C11—H11C | 109.5 |
C2—C3—H3 | 119.2 | H11B—C11—H11C | 109.5 |
C4—C3—H3 | 119.2 | C10—O2—C11 | 116.00 (16) |
O3—C7—N1 | 124.79 (18) | C9—C12—H12A | 120.0 |
O3—C7—C6 | 129.47 (18) | C9—C12—H12B | 120.0 |
N1—C7—C6 | 105.73 (15) | H12A—C12—H12B | 120.0 |
O4—C8—N1 | 124.39 (17) | ||
C4—C5—C6—C1 | 0.3 (3) | O4—C8—N1—C7 | −176.95 (18) |
C8—C5—C6—C1 | 179.59 (16) | C5—C8—N1—C7 | 1.5 (2) |
C4—C5—C6—C7 | −178.18 (16) | O4—C8—N1—C9 | 5.0 (3) |
C8—C5—C6—C7 | 1.11 (19) | C5—C8—N1—C9 | −176.60 (15) |
C5—C6—C1—C2 | −0.3 (3) | O3—C7—N1—C8 | −179.88 (18) |
C7—C6—C1—C2 | 177.86 (18) | C6—C7—N1—C8 | −0.8 (2) |
C6—C1—C2—C3 | 0.3 (3) | O3—C7—N1—C9 | −1.9 (3) |
C6—C5—C4—C3 | −0.3 (3) | C6—C7—N1—C9 | 177.20 (15) |
C8—C5—C4—C3 | −179.41 (19) | C8—N1—C9—C12 | −137.6 (2) |
C1—C2—C3—C4 | −0.3 (3) | C7—N1—C9—C12 | 44.7 (3) |
C5—C4—C3—C2 | 0.3 (3) | C8—N1—C9—C10 | 50.6 (2) |
C1—C6—C7—O3 | 0.5 (3) | C7—N1—C9—C10 | −127.22 (19) |
C5—C6—C7—O3 | 178.8 (2) | C12—C9—C10—O1 | −142.1 (2) |
C1—C6—C7—N1 | −178.55 (18) | N1—C9—C10—O1 | 29.7 (3) |
C5—C6—C7—N1 | −0.22 (19) | C12—C9—C10—O2 | 36.7 (3) |
C4—C5—C8—O4 | −4.1 (3) | N1—C9—C10—O2 | −151.46 (16) |
C6—C5—C8—O4 | 176.72 (19) | O1—C10—O2—C11 | 0.8 (3) |
C4—C5—C8—N1 | 177.62 (18) | C9—C10—O2—C11 | −178.04 (17) |
C6—C5—C8—N1 | −1.57 (19) |
Experimental details
Crystal data | |
Chemical formula | C12H9NO4 |
Mr | 231.20 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 294 |
a, b, c (Å) | 6.5179 (3), 7.4817 (4), 11.7322 (6) |
α, β, γ (°) | 80.954 (2), 78.866 (2), 76.723 (2) |
V (Å3) | 542.52 (5) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.11 |
Crystal size (mm) | 0.20 × 0.18 × 0.15 |
Data collection | |
Diffractometer | Bruker APEX CCD area-detector |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.979, 0.984 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 2932, 1984, 1497 |
Rint | 0.016 |
(sin θ/λ)max (Å−1) | 0.606 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.041, 0.114, 1.04 |
No. of reflections | 1984 |
No. of parameters | 156 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.18, −0.14 |
Computer programs: SMART (Bruker, 2000), SAINT (Bruker, 2000), SHELXL97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 2000).
Acknowledgements
We acknowledge financial support from the Research Fund for the new faculty at the State Key Laboratory of Applied Organic Chemstry.
References
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Optical active nonproteinogenic amino acids (Clausen et al., 2002) are valuable compounds of high interest not only due to their remarkable pharmacological and biological activities but also for their role as a topographic probe for investigation of bioactive conformations of peptides and the mechanisms of enzyme reactions. Consequently, efficient and convenient methods for the preparation of optically pure enantiomers of amino acids are be general interest (Cativiela & Diaz-de-Villegas, 2000; Wirth, 1997). It is noteworthy that extraordinary progress has been made in the asymmetric hydrogenation of dehydroamino acids (Osborn et al., 1966; Schmidt et al., 1988), which serve as important precursors of saturated ones.
The title compound belong to one of dehydroamino acids mentioned above. Its molecular structure is shown in Fig.1 and can be prepared conveniently through nucleophilic addition of phthalimide to propiolate according to the precedent procedure (Trost & Dake, 1997). The exceptionally large difference (Δ δ= 0.68 p.p.m.) between the chemical shifts of the two protons (Ha and Hb) on the double bond suggest that the chemical environments (e.g., deshielding effect of the phthalimidyl group) of them are considerably different. As shown in Fig. 1, An s-trans conformation is observed, which was discussed in detail other groups previously (Ajò et al., 1984; Ajò et al., 1979; Busetti, et al., 1984; Busetti, et al., 1986). The double bond (C9–C12) is not parallel with the carbonyl (C10–O1) group with the C12-C9_C10-O1 torsion angle -142.3 (2)° while the double bond (C9–C12) lies out of the plane of the phthalimidyl group with the torsion angle C7—N1—C9—C12 44.7 (3)°.