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accessN4,N6-Dimethyl-N4,N6-diphenylpyrimidine-4,5,6-triamine
aSchool of Chemical Engineering, Changchun University of Technology, Changchun 130012, People's Republic of China, and bSchool of Bioscience and Technology, Changchun University, Changchun 130012, People's Republic of China
*Correspondence e-mail: fly012345@sohu.com
In the title compound, C18H19N5, the pyrimidine ring makes dihedral angles of 56.49 (9) and 70.88 (9)° with the phenyl rings. The dihedral angle between the two phenyl rings is 72.45 (9)°. No significant intermolecular interactions are observed in the crystal structure.
Related literature
For applications and the biological activity of pyrimidine triamines, see: Barillari et al. (2001![[Barillari, C., Barlocco, D. & Raveglia, L. (2001). Eur. J. Org. Chem. pp. 4737-4741.]](../../../../../../logos/arrows/e_arr.gif "Barillari, C., Barlocco, D. & Raveglia, L. (2001). Eur. J. Org. Chem. pp. 4737-4741.")
); Itoh et al. (2004); Koppel & Robins (1958).
![[Scheme 1]](is2800scheme1.gif)
Experimental
Crystal data
|
Data collection: PROCESS-AUTO (Rigaku, 1998); cell PROCESS-AUTO; data reduction: CrystalStructure (Rigaku/MSC, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 2000); software used to prepare material for publication: SHELXL97.
Supporting information
contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536811046642/is2800sup1.cif
Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536811046642/is2800Isup2.hkl
Supporting information file. DOI: https://doi.org/10.1107/S1600536811046642/is2800Isup3.cml
N4,N6-dimethyl-5-nitro-N4,N6 -diphenylpyrimidine-4, 6-diamine (502.5 mg, 1.5 mmol) was dissolved in a mixture of ethanol (16 mL) and water (4 mL). Then, iron powder (504 mg, 9 mmol) and NH4Cl (96.3 mg, 1.8 mmol) were added. The mixture was then stirred in reflux for 6 h, cooled to room temperature, and filtered through a pad of celite. The filtrate was concentrated in vacuo. The residue was extracted with EtOAc, and the organic extract was washed with saturated NaHCO3, water, and brine and dried over anhydrous MgSO4. It was then filtered and concentrated in vacuo to the crude product which was purified by flash (elution with 9% EtOAc in petroleum ether followed by 20% EtOAc in petroleum ether) to give N4,N6-dimethyl-N4,N6- diphenylpyrimidine-4,5,6-triamine (colorless solid, 310 mg, 67.8%, 88.6-90.6 °C).
All H atoms were located from difference Fourier maps and then were treated as riding, with C—H = 0.93–0.96 Å and N—H = 0.86 Å, and with Uiso(H) = 1.2Ueq(C or N) or 1.5Ueq(methyl C).
Pyrimidine triamines not only exhibit a wide range of biological activities (Barillari et al., 2001), but also are important intermediate products (Koppel & Robins, 1958; Itoh et al., 2004). Here, the of N4,N6-dimethyl-N4,N6- diphenylpyrimidine-4,5,6-triamine is reported.
For applications and the biological activity of pyrimidine triamines, see: Barillari et al. (2001); Itoh et al. (2004); Koppel & Robins (1958).
Data collection: PROCESS-AUTO (Rigaku, 1998); cell PROCESS-AUTO (Rigaku, 1998); data reduction: CrystalStructure (Rigaku/MSC, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 2000); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).
![[Figure 1]](./is2800fig1thm.gif) | Fig. 1. The molecular structure of the title compound, with the atom-labelling scheme. Displacement ellipsoid are shown at the 50% probability level. |
| C18H19N5 | F(000) = 1296 |
| Mr = 305.38 | Dx = 1.266 Mg m−3 |
| Orthorhombic, Pbca | Mo Kα radiation, λ = 0.71073 Å |
| Hall symbol: -P 2ac 2ab | Cell parameters from 1000 reflections |
| a = 8.8859 (18) Å | θ = 3.2–27.5° |
| b = 14.360 (3) Å | µ = 0.08 mm−1 |
| c = 25.121 (5) Å | T = 293 K |
| V = 3205.4 (11) Å3 | Block, colorless |
| Z = 8 | 0.32 × 0.28 × 0.22 mm |
| Rigaku R-AXIS RAPID diffractometer | 3664 independent reflections |
| Radiation source: fine-focus sealed tube | 2119 reflections with I > 2σ(I) |
| Graphite monochromator | Rint = 0.065 |
| Detector resolution: 10.00 pixels mm-1 | θmax = 27.5°, θmin = 3.2° |
| ω scans | h = −11→10 |
| Absorption correction: multi-scan (ABSCOR; Higashi, 1995) | k = −18→18 |
| Tmin = 0.975, Tmax = 0.983 | l = −32→32 |
| 28152 measured reflections |
| 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)] = 0.052 | Hydrogen site location: inferred from neighbouring sites |
| wR(F2) = 0.137 | H-atom parameters constrained |
| S = 1.03 | w = 1/[σ2(Fo2) + (0.0693P)2] where P = (Fo2 + 2Fc2)/3 |
| 3664 reflections | (Δ/σ)max < 0.001 |
| 210 parameters | Δρmax = 0.13 e Å−3 |
| 0 restraints | Δρmin = −0.18 e Å−3 |
| C18H19N5 | V = 3205.4 (11) Å3 |
| Mr = 305.38 | Z = 8 |
| Orthorhombic, Pbca | Mo Kα radiation |
| a = 8.8859 (18) Å | µ = 0.08 mm−1 |
| b = 14.360 (3) Å | T = 293 K |
| c = 25.121 (5) Å | 0.32 × 0.28 × 0.22 mm |
| Rigaku R-AXIS RAPID diffractometer | 3664 independent reflections |
| Absorption correction: multi-scan (ABSCOR; Higashi, 1995) | 2119 reflections with I > 2σ(I) |
| Tmin = 0.975, Tmax = 0.983 | Rint = 0.065 |
| 28152 measured reflections |
| R[F2 > 2σ(F2)] = 0.052 | 0 restraints |
| wR(F2) = 0.137 | H-atom parameters constrained |
| S = 1.03 | Δρmax = 0.13 e Å−3 |
| 3664 reflections | Δρmin = −0.18 e Å−3 |
| 210 parameters |
Experimental. 1H NMR (CDCl3, 400 Hz), δ: 8.38 (s, 1H), 7.27 (t, J = 7.6Hz, 4H), 7.00(t, J = 7.2Hz, 2H), 6.90(d, J = 8.0Hz, 4H), 3.50 (s, 6H); 2.90 (s, 2H). 13C NMR (CDCl3, 100 Hz), δ: 151.1, 148.0, 145.7, 129.3, 122.8, 122.7, 120.0, 39.7. ES-MS: 336.1 [(M + H+)]. |
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. |
| x | y | z | Uiso*/Ueq | ||
| C1 | −0.0279 (3) | 0.46280 (13) | 0.41196 (8) | 0.0660 (6) | |
| H1 | −0.0833 | 0.5128 | 0.4249 | 0.079* | |
| C2 | 0.0751 (2) | 0.32120 (11) | 0.42746 (6) | 0.0483 (4) | |
| C3 | 0.15006 (19) | 0.32587 (11) | 0.37827 (6) | 0.0460 (4) | |
| C4 | 0.1152 (2) | 0.40201 (11) | 0.34631 (6) | 0.0484 (4) | |
| C5 | 0.1622 (2) | 0.34917 (11) | 0.25472 (6) | 0.0480 (4) | |
| C6 | 0.0766 (2) | 0.26882 (12) | 0.26084 (7) | 0.0563 (5) | |
| H6 | 0.0287 | 0.2573 | 0.2931 | 0.068* | |
| C7 | 0.0620 (2) | 0.20590 (13) | 0.21954 (8) | 0.0626 (5) | |
| H7 | 0.0059 | 0.1519 | 0.2245 | 0.075* | |
| C8 | 0.1296 (2) | 0.22228 (16) | 0.17087 (8) | 0.0689 (6) | |
| H8 | 0.1205 | 0.1795 | 0.1433 | 0.083* | |
| C9 | 0.2099 (2) | 0.30237 (15) | 0.16412 (8) | 0.0679 (6) | |
| H9 | 0.2534 | 0.3148 | 0.1312 | 0.082* | |
| C10 | 0.2278 (2) | 0.36518 (14) | 0.20496 (7) | 0.0586 (5) | |
| H10 | 0.2842 | 0.4189 | 0.1994 | 0.070* | |
| C11 | 0.0814 (2) | 0.15421 (10) | 0.44409 (6) | 0.0478 (4) | |
| C12 | 0.1647 (2) | 0.08195 (13) | 0.46579 (7) | 0.0612 (5) | |
| H12 | 0.2369 | 0.0943 | 0.4917 | 0.073* | |
| C13 | 0.1404 (3) | −0.00819 (13) | 0.44895 (9) | 0.0713 (6) | |
| H13 | 0.1949 | −0.0566 | 0.4642 | 0.086* | |
| C14 | 0.0367 (3) | −0.02727 (13) | 0.40991 (9) | 0.0732 (6) | |
| H14 | 0.0223 | −0.0882 | 0.3983 | 0.088* | |
| C15 | −0.0447 (3) | 0.04322 (13) | 0.38829 (8) | 0.0688 (6) | |
| H15 | −0.1150 | 0.0305 | 0.3619 | 0.083* | |
| C16 | −0.0238 (2) | 0.13385 (12) | 0.40531 (7) | 0.0570 (5) | |
| H16 | −0.0810 | 0.1815 | 0.3905 | 0.068* | |
| C17 | 0.2467 (3) | 0.50505 (12) | 0.28371 (9) | 0.0743 (6) | |
| H17A | 0.3482 | 0.4977 | 0.2713 | 0.111* | |
| H17B | 0.2464 | 0.5430 | 0.3152 | 0.111* | |
| H17C | 0.1874 | 0.5345 | 0.2566 | 0.111* | |
| C18 | 0.0744 (4) | 0.26304 (14) | 0.51905 (7) | 0.0931 (9) | |
| H18A | 0.1106 | 0.3236 | 0.5290 | 0.140* | |
| H18B | 0.1257 | 0.2163 | 0.5395 | 0.140* | |
| H18C | −0.0318 | 0.2593 | 0.5258 | 0.140* | |
| N1 | 0.02716 (19) | 0.47211 (9) | 0.36360 (6) | 0.0593 (4) | |
| N2 | −0.01344 (19) | 0.39000 (10) | 0.44460 (6) | 0.0602 (4) | |
| N3 | 0.18291 (19) | 0.41347 (9) | 0.29607 (6) | 0.0578 (4) | |
| N4 | 0.25718 (18) | 0.26103 (9) | 0.36391 (6) | 0.0583 (4) | |
| H4A | 0.3049 | 0.2669 | 0.3343 | 0.070* | |
| H4B | 0.2762 | 0.2147 | 0.3845 | 0.070* | |
| N5 | 0.1029 (2) | 0.24762 (9) | 0.46223 (5) | 0.0568 (4) |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| C1 | 0.0737 (15) | 0.0553 (10) | 0.0688 (13) | 0.0106 (10) | 0.0113 (11) | −0.0102 (9) |
| C2 | 0.0550 (11) | 0.0480 (9) | 0.0419 (9) | −0.0040 (8) | −0.0006 (8) | −0.0048 (7) |
| C3 | 0.0475 (10) | 0.0451 (8) | 0.0454 (9) | −0.0010 (8) | 0.0001 (8) | −0.0040 (7) |
| C4 | 0.0528 (11) | 0.0448 (8) | 0.0475 (10) | −0.0015 (8) | −0.0008 (8) | −0.0016 (7) |
| C5 | 0.0473 (10) | 0.0530 (9) | 0.0437 (9) | 0.0073 (8) | −0.0007 (7) | 0.0038 (7) |
| C6 | 0.0542 (11) | 0.0653 (11) | 0.0493 (10) | −0.0004 (9) | 0.0027 (9) | 0.0004 (8) |
| C7 | 0.0603 (13) | 0.0644 (11) | 0.0631 (12) | 0.0040 (10) | −0.0090 (10) | −0.0071 (9) |
| C8 | 0.0674 (14) | 0.0877 (14) | 0.0517 (12) | 0.0182 (12) | −0.0070 (10) | −0.0156 (10) |
| C9 | 0.0669 (14) | 0.0877 (14) | 0.0492 (11) | 0.0198 (12) | 0.0063 (10) | −0.0004 (10) |
| C10 | 0.0547 (12) | 0.0690 (11) | 0.0522 (11) | 0.0099 (9) | 0.0064 (9) | 0.0093 (9) |
| C11 | 0.0520 (10) | 0.0490 (9) | 0.0425 (9) | −0.0001 (8) | 0.0037 (8) | 0.0017 (7) |
| C12 | 0.0571 (12) | 0.0726 (12) | 0.0540 (11) | 0.0066 (10) | 0.0002 (9) | 0.0098 (9) |
| C13 | 0.0785 (16) | 0.0578 (11) | 0.0776 (14) | 0.0206 (11) | 0.0180 (12) | 0.0118 (10) |
| C14 | 0.0905 (18) | 0.0519 (11) | 0.0770 (15) | −0.0024 (11) | 0.0167 (13) | −0.0077 (10) |
| C15 | 0.0737 (15) | 0.0623 (12) | 0.0703 (13) | −0.0102 (11) | −0.0048 (11) | −0.0086 (10) |
| C16 | 0.0578 (12) | 0.0547 (10) | 0.0585 (11) | 0.0006 (9) | −0.0063 (9) | 0.0003 (8) |
| C17 | 0.0932 (17) | 0.0561 (11) | 0.0734 (14) | −0.0147 (11) | 0.0105 (12) | 0.0092 (9) |
| C18 | 0.164 (3) | 0.0758 (13) | 0.0391 (11) | −0.0086 (15) | 0.0004 (13) | −0.0048 (9) |
| N1 | 0.0656 (11) | 0.0511 (8) | 0.0611 (10) | 0.0072 (8) | 0.0001 (8) | −0.0028 (7) |
| N2 | 0.0707 (11) | 0.0551 (8) | 0.0548 (9) | 0.0016 (8) | 0.0109 (8) | −0.0073 (7) |
| N3 | 0.0740 (12) | 0.0528 (8) | 0.0466 (8) | −0.0090 (8) | 0.0073 (7) | 0.0052 (6) |
| N4 | 0.0607 (10) | 0.0602 (9) | 0.0542 (9) | 0.0132 (8) | 0.0116 (8) | 0.0062 (7) |
| N5 | 0.0807 (12) | 0.0530 (8) | 0.0366 (8) | −0.0063 (8) | −0.0048 (7) | −0.0014 (6) |
| C1—N1 | 1.316 (2) | C11—C16 | 1.381 (2) |
| C1—N2 | 1.335 (2) | C11—C12 | 1.386 (2) |
| C1—H1 | 0.9300 | C11—N5 | 1.429 (2) |
| C2—N2 | 1.334 (2) | C12—C13 | 1.379 (3) |
| C2—N5 | 1.393 (2) | C12—H12 | 0.9300 |
| C2—C3 | 1.406 (2) | C13—C14 | 1.374 (3) |
| C3—N4 | 1.379 (2) | C13—H13 | 0.9300 |
| C3—C4 | 1.391 (2) | C14—C15 | 1.357 (3) |
| C4—N1 | 1.347 (2) | C14—H14 | 0.9300 |
| C4—N3 | 1.408 (2) | C15—C16 | 1.383 (2) |
| C5—C6 | 1.391 (2) | C15—H15 | 0.9300 |
| C5—C10 | 1.398 (2) | C16—H16 | 0.9300 |
| C5—N3 | 1.402 (2) | C17—N3 | 1.465 (2) |
| C6—C7 | 1.382 (2) | C17—H17A | 0.9600 |
| C6—H6 | 0.9300 | C17—H17B | 0.9600 |
| C7—C8 | 1.382 (3) | C17—H17C | 0.9600 |
| C7—H7 | 0.9300 | C18—N5 | 1.466 (2) |
| C8—C9 | 1.364 (3) | C18—H18A | 0.9600 |
| C8—H8 | 0.9300 | C18—H18B | 0.9600 |
| C9—C10 | 1.375 (3) | C18—H18C | 0.9600 |
| C9—H9 | 0.9300 | N4—H4A | 0.8600 |
| C10—H10 | 0.9300 | N4—H4B | 0.8600 |
| N1—C1—N2 | 127.64 (17) | C14—C13—C12 | 120.75 (19) |
| N1—C1—H1 | 116.2 | C14—C13—H13 | 119.6 |
| N2—C1—H1 | 116.2 | C12—C13—H13 | 119.6 |
| N2—C2—N5 | 117.64 (15) | C15—C14—C13 | 119.64 (19) |
| N2—C2—C3 | 121.86 (15) | C15—C14—H14 | 120.2 |
| N5—C2—C3 | 120.22 (15) | C13—C14—H14 | 120.2 |
| N4—C3—C4 | 122.23 (15) | C14—C15—C16 | 120.4 (2) |
| N4—C3—C2 | 121.66 (15) | C14—C15—H15 | 119.8 |
| C4—C3—C2 | 116.04 (15) | C16—C15—H15 | 119.8 |
| N1—C4—C3 | 122.05 (15) | C11—C16—C15 | 120.57 (17) |
| N1—C4—N3 | 116.75 (14) | C11—C16—H16 | 119.7 |
| C3—C4—N3 | 120.91 (16) | C15—C16—H16 | 119.7 |
| C6—C5—C10 | 117.61 (16) | N3—C17—H17A | 109.5 |
| C6—C5—N3 | 122.42 (15) | N3—C17—H17B | 109.5 |
| C10—C5—N3 | 119.97 (16) | H17A—C17—H17B | 109.5 |
| C7—C6—C5 | 120.74 (17) | N3—C17—H17C | 109.5 |
| C7—C6—H6 | 119.6 | H17A—C17—H17C | 109.5 |
| C5—C6—H6 | 119.6 | H17B—C17—H17C | 109.5 |
| C6—C7—C8 | 120.78 (19) | N5—C18—H18A | 109.5 |
| C6—C7—H7 | 119.6 | N5—C18—H18B | 109.5 |
| C8—C7—H7 | 119.6 | H18A—C18—H18B | 109.5 |
| C9—C8—C7 | 118.74 (18) | N5—C18—H18C | 109.5 |
| C9—C8—H8 | 120.6 | H18A—C18—H18C | 109.5 |
| C7—C8—H8 | 120.6 | H18B—C18—H18C | 109.5 |
| C8—C9—C10 | 121.40 (19) | C1—N1—C4 | 115.94 (15) |
| C8—C9—H9 | 119.3 | C2—N2—C1 | 116.00 (16) |
| C10—C9—H9 | 119.3 | C5—N3—C4 | 122.09 (14) |
| C9—C10—C5 | 120.70 (19) | C5—N3—C17 | 118.99 (15) |
| C9—C10—H10 | 119.7 | C4—N3—C17 | 117.41 (14) |
| C5—C10—H10 | 119.7 | C3—N4—H4A | 120.0 |
| C16—C11—C12 | 118.70 (16) | C3—N4—H4B | 120.0 |
| C16—C11—N5 | 120.91 (15) | H4A—N4—H4B | 120.0 |
| C12—C11—N5 | 120.38 (16) | C2—N5—C11 | 119.23 (13) |
| C13—C12—C11 | 119.90 (19) | C2—N5—C18 | 117.72 (15) |
| C13—C12—H12 | 120.0 | C11—N5—C18 | 115.39 (14) |
| C11—C12—H12 | 120.0 |
Experimental details
| Crystal data | |
| Chemical formula | C18H19N5 |
| Mr | 305.38 |
| Crystal system, space group | Orthorhombic, Pbca |
| Temperature (K) | 293 |
| a, b, c (Å) | 8.8859 (18), 14.360 (3), 25.121 (5) |
| V (Å3) | 3205.4 (11) |
| Z | 8 |
| Radiation type | Mo Kα |
| µ (mm−1) | 0.08 |
| Crystal size (mm) | 0.32 × 0.28 × 0.22 |
| Data collection | |
| Diffractometer | Rigaku R-AXIS RAPID |
| Absorption correction | Multi-scan (ABSCOR; Higashi, 1995) |
| Tmin, Tmax | 0.975, 0.983 |
| No. of measured, independent and observed [I > 2σ(I)] reflections | 28152, 3664, 2119 |
| Rint | 0.065 |
| (sin θ/λ)max (Å−1) | 0.649 |
| Refinement | |
| R[F2 > 2σ(F2)], wR(F2), S | 0.052, 0.137, 1.03 |
| No. of reflections | 3664 |
| No. of parameters | 210 |
| H-atom treatment | H-atom parameters constrained |
| Δρmax, Δρmin (e Å−3) | 0.13, −0.18 |
Computer programs: PROCESS-AUTO (Rigaku, 1998), CrystalStructure (Rigaku/MSC, 2002), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), DIAMOND (Brandenburg, 2000).
Acknowledgements
The project was sponsored by the Scientific Research Foundation for Returned Overseas Chinese Scholars, the State Education Ministry (20071108) and the Scientific Research Foundation for the Returned Overseas Team, Chinese Education Ministry.
References
Barillari, C., Barlocco, D. & Raveglia, L. (2001). Eur. J. Org. Chem. pp. 4737–4741. CrossRef Google Scholar
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| CRYSTALLOGRAPHIC COMMUNICATIONS |
Pyrimidine triamines not only exhibit a wide range of biological activities (Barillari et al., 2001), but also are important intermediate products (Koppel & Robins, 1958; Itoh et al., 2004). Here, the crystal structure of N4,N6-dimethyl-N4,N6- diphenylpyrimidine-4,5,6-triamine is reported.