Acta Cryst. (2007). E63, o4023 [ doi:10.1107/S1600536807043644 ]
The title compound, C24H19N3O3S, is the result of a diastereoselective aziridination reaction performed on the corresponding Reissert adduct (1-benzoyl-1,2-dihydroquinoline-2-carbonitrile). The aziridine ring is trans disposed to the nitrile group.
To a solution of 1-benzoyl-1,2-dihydroquinoline-2-carbonitrile (855 mg, 4.0 mmol) in dry CH3CN (14 ml), Cu(acac)2 (524 mg, 2.0 mmol) and PhI=NTs (10.4 g, 27.9 mmol) were added at room temperature. After 2 minutes of vigorous stirring, the temperature of the reaction mixture increased significantly and the initial blue suspension turned brown. The mixture was then allowed to cool to room temperature, filtered through a pad of silica and the filter cake was rinsed thoroughly with CH2Cl2. The filtrate was then concentrated in vacuo and the resulting solid was recrystallized in methylene chloride. The obtained crystals were filtered off. After being kept for 1 h at RT, the organic layer was filtered again. The resulting filtrate was concentrated in vacuo and the crude product was purified by silica gel chromatography (eluting with CH2Cl2) to afford (I) as a white solid in a 70% yield (1.2 g, 2.8 mmol). Single crystals of (I) suitable for X-ray analysis were obtained by slow crystallization from CH2Cl2/petroleum ether, at room temperature and without evaporation (m.p. 459 K).
C—H H atoms were positioned with idealized geometry and were refined isotropic (Uiso(H) = 1.2× Ueq(C)) using a riding model. The O—H H atoms were located in difference map syntheses and were refined isotropic (Uiso(H) = 1.2× Ueq(O)) with varying coordinates.
Data collection: COLLECT (Nonius, 1998); cell refinement: EVALCCD (Duisenberg et al., 2003); data reduction: COLLECT (Nonius, 1998); program(s) used to solve structure: SIR2002 (Burla et al., 2003); program(s) used to refine structure: JANA2006 (Petricek et al., 2006); molecular graphics: DIAMOND (Brandenburg & Putz, 2005); software used to prepare material for publication: JANA2006 (Petricek et al., 2006).
![[Figure 1]](./nc2055fig1thm.gif)
| Fig. 1. Molecular structure showing 30% probability displacement ellipsoids. H atoms are omitted for clarity. |
| C24H19N3O3S | V = 1102.36 (11) Å3 |
| Mr = 429.5 | Z = 2 |
| Triclinic, P1 | F000 = 448 |
| Hall symbol: -P 1 | Dx = 1.294 Mg m−3 |
| a = 8.7215 (5) Å | Mo Kα radiation λ = 0.71069 Å |
| b = 12.1042 (4) Å | µ = 0.18 mm−1 |
| c = 12.4678 (7) Å | T = 293 K |
| α = 64.267 (3)º | Thick plate, colourless |
| β = 69.759 (5)º | 0.6 × 0.3 × 0.09 mm |
| γ = 87.895 (3)º |
| Nonius KappaCCD diffractometer | 6242 independent reflections |
| Radiation source: X-ray tube | 4445 reflections with I > 2σ(I) |
| Monochromator: horizonally mounted graphite crystal | Rint = 0.055 |
| Detector resolution: 9 pixels mm-1 | θmax = 30.0º |
| T = 293 K | θmin = 6.5º |
| CCD, φ and ω frames scans | h = −12→11 |
| Absorption correction: Gaussian (JANA2006; Petricek et al., 2006) | k = −17→16 |
| Tmin = 0.922, Tmax = 0.977 | l = −17→17 |
| 34014 measured reflections |
| Refinement on F2 | H-atom parameters constrained |
| R[F2 > 2σ(F2)] = 0.066 | Weighting scheme based on measured s.u.'s w = 1/(σ2(I) + 0.001936I2) |
| wR(F2) = 0.157 | (Δ/σ)max = 0.001 |
| S = 2.06 | Δρmax = 0.36 e Å−3 |
| 6242 reflections | Δρmin = −0.36 e Å−3 |
| 280 parameters | Extinction correction: none |
| 76 restraints |
| C24H19N3O3S | γ = 87.895 (3)º |
| Mr = 429.5 | V = 1102.36 (11) Å3 |
| Triclinic, P1 | Z = 2 |
| a = 8.7215 (5) Å | Mo Kα |
| b = 12.1042 (4) Å | µ = 0.18 mm−1 |
| c = 12.4678 (7) Å | T = 293 K |
| α = 64.267 (3)º | 0.6 × 0.3 × 0.09 mm |
| β = 69.759 (5)º |
| Nonius KappaCCD diffractometer | 6242 independent reflections |
| Absorption correction: Gaussian (JANA2006; Petricek et al., 2006) | 4445 reflections with I > 2σ(I) |
| Tmin = 0.922, Tmax = 0.977 | Rint = 0.055 |
| 34014 measured reflections |
| R[F2 > 2σ(F2)] = 0.066 | 76 restraints |
| wR(F2) = 0.157 | H-atom parameters constrained |
| S = 2.06 | Δρmax = 0.36 e Å−3 |
| 6242 reflections | Δρmin = −0.36 e Å−3 |
| 280 parameters |
| x | y | z | Uiso*/Ueq | ||
| S | 0.03291 (6) | 0.08922 (4) | 0.64456 (4) | 0.0454 (2) | |
| N1 | 0.38331 (17) | 0.30804 (12) | 0.24992 (13) | 0.0384 (6) | |
| N2 | 0.4895 (3) | 0.0724 (2) | 0.1684 (2) | 0.0835 (12) | |
| N3 | 0.18953 (17) | 0.17068 (13) | 0.50524 (13) | 0.0390 (6) | |
| O1 | 0.2135 (2) | 0.41987 (14) | 0.15447 (16) | 0.0669 (9) | |
| O2 | −0.11266 (16) | 0.12656 (15) | 0.61889 (14) | 0.0612 (8) | |
| O3 | 0.04832 (19) | −0.04033 (13) | 0.69441 (14) | 0.0638 (7) | |
| C1 | 0.4044 (3) | 0.12536 (18) | 0.21482 (18) | 0.0519 (9) | |
| C2 | 0.2965 (2) | 0.18988 (15) | 0.28240 (16) | 0.0402 (7) | |
| C3 | 0.2444 (2) | 0.10530 (15) | 0.42537 (16) | 0.0403 (7) | |
| C4 | 0.3496 (2) | 0.11772 (15) | 0.49134 (16) | 0.0399 (7) | |
| C5 | 0.5036 (2) | 0.20893 (15) | 0.41258 (16) | 0.0383 (7) | |
| C6 | 0.6338 (2) | 0.20193 (17) | 0.45378 (19) | 0.0472 (9) | |
| C7 | 0.7791 (2) | 0.28230 (19) | 0.3736 (2) | 0.0548 (10) | |
| C8 | 0.7955 (2) | 0.36839 (19) | 0.2523 (2) | 0.0545 (10) | |
| C9 | 0.6662 (2) | 0.37820 (17) | 0.20927 (18) | 0.0456 (8) | |
| C10 | 0.5196 (2) | 0.29989 (15) | 0.29066 (16) | 0.0371 (7) | |
| C11 | 0.3119 (2) | 0.41407 (16) | 0.20566 (17) | 0.0426 (8) | |
| C12 | 0.3561 (2) | 0.51944 (17) | 0.22680 (18) | 0.0434 (8) | |
| C13 | 0.3917 (2) | 0.63836 (18) | 0.1289 (2) | 0.0573 (10) | |
| C14 | 0.4231 (3) | 0.7372 (2) | 0.1500 (3) | 0.0724 (12) | |
| C15 | 0.4171 (3) | 0.7182 (2) | 0.2673 (3) | 0.0734 (14) | |
| C16 | 0.3781 (3) | 0.6006 (2) | 0.3665 (3) | 0.0701 (14) | |
| C17 | 0.3481 (3) | 0.5005 (2) | 0.3467 (2) | 0.0570 (10) | |
| C18 | 0.0664 (2) | 0.14759 (17) | 0.74182 (17) | 0.0442 (8) | |
| C19 | 0.1465 (3) | 0.0827 (2) | 0.82352 (19) | 0.0556 (10) | |
| C20 | 0.1657 (3) | 0.1281 (2) | 0.9038 (2) | 0.0664 (11) | |
| C21 | 0.1063 (3) | 0.2348 (2) | 0.90398 (19) | 0.0602 (10) | |
| C22 | 0.0286 (3) | 0.2989 (2) | 0.8193 (2) | 0.0716 (14) | |
| C23 | 0.0073 (3) | 0.2564 (2) | 0.7379 (2) | 0.0623 (12) | |
| C24 | 0.1240 (4) | 0.2816 (3) | 0.9939 (3) | 0.0935 (16) | |
| H1 | 0.203733 | 0.20999 | 0.254501 | 0.0483* | |
| H2 | 0.199338 | 0.03397 | 0.424107 | 0.0484* | |
| H3 | 0.398591 | 0.05981 | 0.548829 | 0.0479* | |
| H4 | 0.623121 | 0.140591 | 0.539025 | 0.0567* | |
| H5 | 0.869957 | 0.27826 | 0.402578 | 0.0657* | |
| H6 | 0.899022 | 0.422553 | 0.196621 | 0.0654* | |
| H7 | 0.678118 | 0.438968 | 0.123512 | 0.0548* | |
| H8 | 0.394574 | 0.652419 | 0.045403 | 0.0688* | |
| H9 | 0.449713 | 0.821142 | 0.081592 | 0.0869* | |
| H10 | 0.44065 | 0.788185 | 0.280272 | 0.088* | |
| H11 | 0.371761 | 0.588293 | 0.450215 | 0.0841* | |
| H12 | 0.321681 | 0.417394 | 0.416576 | 0.0684* | |
| H13 | 0.188175 | 0.006955 | 0.824521 | 0.0667* | |
| H14 | 0.222353 | 0.083944 | 0.961486 | 0.0797* | |
| H15 | −0.011942 | 0.375303 | 0.816864 | 0.0859* | |
| H16 | −0.047788 | 0.301988 | 0.679431 | 0.0748* | |
| H17 | 0.030292 | 0.328238 | 1.014529 | 0.1122* | |
| H18 | 0.122915 | 0.209872 | 1.074466 | 0.1122* | |
| H19 | 0.230573 | 0.337637 | 0.952164 | 0.1122* |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| S | 0.0484 (3) | 0.0468 (3) | 0.0412 (2) | −0.00713 (18) | −0.01196 (18) | −0.0223 (2) |
| N1 | 0.0433 (7) | 0.0354 (7) | 0.0410 (7) | 0.0015 (6) | −0.0209 (6) | −0.0167 (6) |
| N2 | 0.1091 (17) | 0.0649 (13) | 0.0662 (13) | 0.0108 (12) | −0.0106 (12) | −0.0371 (11) |
| N3 | 0.0449 (8) | 0.0370 (7) | 0.0382 (7) | 0.0010 (6) | −0.0151 (6) | −0.0194 (6) |
| O1 | 0.0785 (10) | 0.0601 (9) | 0.0908 (11) | 0.0173 (7) | −0.0626 (9) | −0.0350 (9) |
| O2 | 0.0460 (7) | 0.0875 (11) | 0.0615 (9) | −0.0034 (7) | −0.0203 (6) | −0.0419 (8) |
| O3 | 0.0841 (10) | 0.0413 (8) | 0.0518 (8) | −0.0131 (6) | −0.0115 (7) | −0.0173 (6) |
| C1 | 0.0706 (13) | 0.0428 (10) | 0.0406 (10) | −0.0025 (9) | −0.0155 (9) | −0.0203 (8) |
| C2 | 0.0473 (9) | 0.0389 (9) | 0.0403 (9) | 0.0002 (7) | −0.0194 (7) | −0.0198 (7) |
| C3 | 0.0511 (9) | 0.0347 (8) | 0.0404 (9) | −0.0012 (7) | −0.0163 (7) | −0.0213 (7) |
| C4 | 0.0498 (9) | 0.0358 (8) | 0.0397 (9) | 0.0079 (7) | −0.0204 (7) | −0.0189 (7) |
| C5 | 0.0441 (9) | 0.0365 (8) | 0.0435 (9) | 0.0081 (6) | −0.0200 (7) | −0.0231 (7) |
| C6 | 0.0565 (11) | 0.0452 (10) | 0.0551 (11) | 0.0146 (8) | −0.0324 (9) | −0.0269 (9) |
| C7 | 0.0468 (10) | 0.0600 (12) | 0.0752 (14) | 0.0122 (9) | −0.0351 (10) | −0.0362 (11) |
| C8 | 0.0417 (10) | 0.0539 (12) | 0.0700 (13) | 0.0019 (8) | −0.0213 (9) | −0.0288 (11) |
| C9 | 0.0432 (9) | 0.0424 (10) | 0.0503 (10) | 0.0009 (7) | −0.0171 (8) | −0.0197 (9) |
| C10 | 0.0388 (8) | 0.0365 (8) | 0.0438 (9) | 0.0066 (6) | −0.0201 (7) | −0.0211 (7) |
| C11 | 0.0441 (9) | 0.0425 (9) | 0.0460 (9) | 0.0047 (7) | −0.0220 (7) | −0.0198 (8) |
| C12 | 0.0411 (9) | 0.0441 (10) | 0.0513 (10) | 0.0091 (7) | −0.0191 (7) | −0.0255 (8) |
| C13 | 0.0661 (13) | 0.0449 (11) | 0.0544 (12) | 0.0037 (9) | −0.0157 (9) | −0.0213 (9) |
| C14 | 0.0865 (17) | 0.0441 (12) | 0.0748 (16) | −0.0027 (11) | −0.0144 (13) | −0.0272 (12) |
| C15 | 0.0778 (15) | 0.0608 (15) | 0.0934 (18) | 0.0045 (11) | −0.0202 (13) | −0.0532 (14) |
| C16 | 0.0884 (16) | 0.0706 (15) | 0.0749 (16) | 0.0185 (12) | −0.0350 (13) | −0.0498 (14) |
| C17 | 0.0729 (13) | 0.0514 (12) | 0.0575 (12) | 0.0137 (10) | −0.0291 (10) | −0.0303 (10) |
| C18 | 0.0431 (9) | 0.0515 (10) | 0.0384 (9) | −0.0032 (7) | −0.0123 (7) | −0.0220 (8) |
| C19 | 0.0618 (12) | 0.0534 (12) | 0.0525 (11) | 0.0030 (9) | −0.0254 (9) | −0.0208 (10) |
| C20 | 0.0790 (15) | 0.0690 (15) | 0.0489 (12) | −0.0123 (11) | −0.0330 (11) | −0.0155 (11) |
| C21 | 0.0654 (13) | 0.0712 (14) | 0.0427 (10) | −0.0187 (10) | −0.0136 (9) | −0.0273 (10) |
| C22 | 0.0804 (16) | 0.0755 (16) | 0.0899 (17) | 0.0158 (12) | −0.0390 (14) | −0.0583 (14) |
| C23 | 0.0741 (14) | 0.0674 (14) | 0.0749 (15) | 0.0198 (11) | −0.0444 (12) | −0.0452 (12) |
| C24 | 0.131 (2) | 0.096 (2) | 0.0582 (15) | −0.0318 (17) | −0.0286 (16) | −0.0393 (15) |
| S—N3 | 1.6809 (12) | C16—C17 | 1.387 (4) |
| S—O2 | 1.4255 (16) | C18—C19 | 1.378 (3) |
| S—O3 | 1.4350 (15) | C18—C23 | 1.384 (3) |
| S—C18 | 1.749 (3) | C19—C20 | 1.390 (4) |
| N1—C2 | 1.465 (3) | C20—C21 | 1.375 (4) |
| N1—C10 | 1.431 (3) | C21—C22 | 1.386 (4) |
| N1—C11 | 1.380 (2) | C21—C24 | 1.509 (5) |
| N2—C1 | 1.134 (4) | C22—C23 | 1.384 (5) |
| N3—C3 | 1.474 (3) | C2—H1 | 0.970 |
| N3—C4 | 1.501 (2) | C3—H2 | 0.970 |
| O1—C11 | 1.218 (3) | C4—H3 | 0.970 |
| C1—C2 | 1.474 (3) | C6—H4 | 0.970 |
| C2—C3 | 1.523 (2) | C7—H5 | 0.970 |
| C3—C4 | 1.477 (3) | C8—H6 | 0.970 |
| C4—C5 | 1.497 (2) | C9—H7 | 0.970 |
| C5—C6 | 1.385 (3) | C13—H8 | 0.970 |
| C5—C10 | 1.398 (2) | C14—H9 | 0.970 |
| C6—C7 | 1.386 (2) | C15—H10 | 0.970 |
| C7—C8 | 1.374 (3) | C16—H11 | 0.970 |
| C8—C9 | 1.388 (3) | C17—H12 | 0.970 |
| C9—C10 | 1.385 (2) | C19—H13 | 0.970 |
| C11—C12 | 1.498 (3) | C20—H14 | 0.970 |
| C12—C13 | 1.380 (2) | C22—H15 | 0.970 |
| C12—C17 | 1.387 (4) | C23—H16 | 0.970 |
| C13—C14 | 1.388 (4) | C24—H17 | 1.000 |
| C14—C15 | 1.360 (5) | C24—H18 | 1.000 |
| C15—C16 | 1.373 (3) | C24—H19 | 1.000 |
| N3—S—O2 | 105.04 (8) | C8—C9—C10 | 119.04 (17) |
| N3—S—O3 | 110.74 (8) | N1—C10—C5 | 118.70 (13) |
| N3—S—C18 | 101.40 (9) | N1—C10—C9 | 120.56 (15) |
| O2—S—O3 | 117.70 (11) | C5—C10—C9 | 120.71 (19) |
| O2—S—C18 | 110.99 (11) | N1—C11—O1 | 120.9 (2) |
| O3—S—C18 | 109.65 (10) | N1—C11—C12 | 117.40 (19) |
| C2—N1—C10 | 115.81 (14) | O1—C11—C12 | 121.66 (18) |
| C2—N1—C11 | 118.48 (16) | C11—C12—C13 | 119.7 (2) |
| C10—N1—C11 | 124.53 (17) | C11—C12—C17 | 120.77 (16) |
| S—N3—C3 | 113.62 (11) | C13—C12—C17 | 119.3 (2) |
| S—N3—C4 | 115.41 (9) | C12—C13—C14 | 120.0 (2) |
| C3—N3—C4 | 59.51 (13) | C13—C14—C15 | 120.5 (2) |
| N2—C1—C2 | 176.4 (3) | C14—C15—C16 | 120.1 (3) |
| N1—C2—C1 | 110.98 (14) | C15—C16—C17 | 120.1 (3) |
| N1—C2—C3 | 110.03 (18) | C12—C17—C16 | 119.87 (19) |
| C1—C2—C3 | 107.33 (14) | S—C18—C19 | 119.53 (18) |
| N3—C3—C2 | 113.77 (14) | S—C18—C23 | 119.17 (19) |
| N3—C3—C4 | 61.15 (13) | C19—C18—C23 | 121.3 (3) |
| C2—C3—C4 | 117.69 (14) | C18—C19—C20 | 118.5 (2) |
| N3—C4—C3 | 59.33 (13) | C19—C20—C21 | 121.8 (2) |
| N3—C4—C5 | 116.36 (13) | C20—C21—C22 | 118.2 (3) |
| C3—C4—C5 | 117.95 (15) | C20—C21—C24 | 121.3 (2) |
| C4—C5—C6 | 122.16 (15) | C22—C21—C24 | 120.5 (3) |
| C4—C5—C10 | 118.65 (18) | C21—C22—C23 | 121.6 (3) |
| C6—C5—C10 | 119.09 (14) | C18—C23—C22 | 118.6 (2) |
| C5—C6—C7 | 120.20 (18) | H17—C24—H18 | 109.5 |
| C6—C7—C8 | 120.2 (2) | H17—C24—H19 | 109.5 |
| C7—C8—C9 | 120.70 (17) | H18—C24—H19 | 109.5 |
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Stereoselective additions to the double bond of 1-benzoyl-1,2-dihydroquinoline-2-carbonitrile (Reissert, 1905) have not been extensively studied in the past decades. Recently, an epoxidation reaction has been performed on an optically active Reissert-type compound (Takamura et al., 2001) resulting in the formation of an epoxide ring trans disposed to the nitrile group.
In the course of an ongoing project directed towards the synthesis of sumanirole, a non-natural compound exhibiting anti-parkinsonian activities (Moon et al., 1993), we were interested in introducing an aziridine ring at the C3—C4 positions of the racemic 1-benzoyl-1,2-dihydroquinoline-2-carbonitrile. Subsequent regioselective opening of this strained ring at its benzylic position would allow installation of the amine functionality found in sumanirole at carbon C3.
The aziridination reaction was performed using PhI=NTs (N-(p-tolylsulfonyl)imino)phenyliodinane (Gillespie, 2001) as a nitrene precursor and Cu(acac)2 as a catalyst (Evans et al., 1991, 1994). The reaction led to the formation of a single diastereoisomer in 70% isolated yield. To ascertain the stereochemical relationships between the two newly created stereogenic carbons (C3 and C4) and the carbon bearing the nitrile group (C2), compound (I) was subjected to X-ray crystal structure analysis.
The molecular structure of (I) reveals the trans relative stereochemistry between the aziridine ring and the nitrile group (Fig. 1).