Regio and Stereo-controlled Rearrangement of 1,2-diaroyl-3-arylaziridines and Synthesis of the Derivatives of N-((Z)-1-oxo-1,3-diphenylprop-2-en-2-yl) benzamide
Heshmat A. Samimi*, Bohari M. Yamin, MarzieSoltani
Faculty of Science, Department of Chemistry, Shahrekord University, P. O. Box 115, Shahrekord , Iran.
bSchool of Chemical Sciences and Food Technology, Universitiy Kebangsaan Malaysia, UKM
43500 Bangi Selangor, Malaysia
General Procedure for Rearrangement of keto-aziridines (1a-f)to N-((Z)-1-oxo-1,3-diaryylprop-2-en-2-yl) benzamide(3a-g). Aroyl chloride (2 mmol) was added dropwise to a solution of aziridines (1) (2 mmol) and triethylamine (0.6 mL) in CH2Cl2 (20 mL) at 0 ºC. After 2 h, diethyl thiourea was added and the mixture was stirred at room temperature. The progress of the reaction was monitored by TLC (EtOAc-Hexane: 1/4)). After completion of the reaction, organic layer was rinsed twice with dilute HCl(10%) and water , then dried with anhydrous Na2SO4.Evaporation of the solvent under reduced pressure and subsequent purification of the residue by column chromatography (silica gel, EtOAc-Hexane: 1/4) provided the derivatives of N-((Z)-1-oxo-1,3-diphenylprop-2-en-2-yl) benzamide 3a-g(67-95%) (Table 1).
N-((Z)-1-oxo-1-phenyl-3-(4-chlorophenyl)prop-2-en-2-yl)-4-nitrobenzamide (3a): Yellow solid, m.p. 187-190˚C; IR (KBr): v (cm-1) 3380, 3091, 1662, 1590, 1482, 1101, 867, 828, 756, 685; 1H NMR (400 MHz, CDCl3): δ 8.37 (br, NH), 8.28 (d, J = 8.8 Hz, 2H), 8.07 (d, J = 8.8 Hz, 2H), 7.83 (dd, J = 1.2, 7.6 Hz, 2H), 7.64 (dt, J = 1.2,7.6 Hz, 1H), 7.52 (t, J = 7.6 Hz, 2H), 7.43 (d, J = 8.4 Hz, 2H), 7.37 (d, J = 8.4 Hz, 2H), 6.88 (s, 1H) ppm; 13C NMR (400MHz, CDCl3): δ 193.8, 163.3, 150.0, 138.3, 136.1, 135.7, 133.1, 132.2, 132.1, 132.0, 130.7, 129.8, 129.2, 128.7, 128.6, 124.0 ppm. Anal.Calcd for C22H15ClN2O4: C, 64.95; H, 3.72; N, 6.89%. Found: C, 64.93; H, 3.75; N, 6.71%.
X-ray crystal structure analysis for3a: formula C22H15ClN2O4, M = 406.81, Yellow crystal 0.30×0.10× 0.10 mm, a = 10.0267 (5), b = 16.1419 (9), c = 23.9254 (14) Å, V = 3872.3(4) Å3, ρcalcd = 1.396 mgcm–3, μ = 0.229 mm–1, Z = 8, orthogonal, λ = 0.71073 A°, T = 301 K, ω and φ scans, 3591 reflections collected (±h, ±k, ±l), [I ≥ 2 σ(I)], , 1959 independent (Rint = 0.0808) and 1852 observed reflections [I ≥2 σ(I)], 267 refined parameters, R = 0.0544, wR2 = 0.1260, max residual electron density 0.251 (–0.373) eÅ–3, Flack parameter 0.0040 (6),. Data set was collected with a Bruker SMART APEX CCD area detector diffractometer, Absorption correction: multi-scan (SADABS; Sheldrick, 1996) School of Chemical Sciences and Food Technology,Universiti Kebangsaan Malaysia, .
N-((Z)-1-oxo-1-phenyl-3-(3-nitrophenyl)prop-2-en-2-yl)-4-nitrobenzamide (3b): Yellow Solid, m.p. 162-165˚C; IR (KBr): v (cm-1) 3323, 3119, 1643, 1620, 1602, 1528, 1484, 1449; 1H NMR (400 MHz, CDCl3): δ 8.63 (br, NH), 8.37-8.35 (m, 2H), 8.26 (d, J = 8.9 Hz, 1H), 8.21-8.16 (m, 2H), 8.07 (t, J = 8.2 Hz, 1H), 7.88 (dd, , J = 7.2, 1.4, Hz,1H), 7.67 (tt, J = 7.5, 1.3, Hz, 1H), 7.56 (t, J = 7.8 Hz, 1H), 7.42-7.33 (m, 1H), ), 7.26-7.13 (m, 4H) ppm; 13C NMR (400MHz, CDCl3): δ 193.4, 163.4, 151.3, 148.7, 135.1, 133.1, 131.3, 130.8, 129.5, 128.8, 128.7, 124.2, 123.8, 123.6, 122.7, 121.7 ppm. Anal.Calcd for C22H15N3O4: C, 63.31; H, 3.62; N, 10.07%. Found: C, 63.28; H, 3.65; N, 10.6%.
N-((Z)-1-oxo-1-phenyl-3-(phenyl)prop-2-en-2-yl)-4-nitrobenzamide (3c): White Solid, m.p. 203-205˚C; IR (KBr): v (cm-1) 3217, 3067, 1666, 1664, 1598, 1525, 1480, 1447; 1H NMR (400 MHz, CDCl3): δ 8.76 (br, NH), 8.29 (d, J = 8.7 Hz, 2H), 8.07 (d, J = 8.6 Hz, 2H), 7.90 (d, J = 7.3 Hz, 2H), 7.62 (t, J = 7.5 Hz, 1H), 7.52-7.48 (m, 4H), 7.43-7.36 (m, 3H), 6.92 (s, 1H) ppm; 13CNMR (400MHz) (CDCl3) δ 193.7, 163.1, 149.9, 138.5, 136.4, 133.5, 133.3, 133.1, 132.9, 129.9, 129.8, 129.4, 128.9, 128.8, 128.5, 123.9 ppm. Anal.Calcd for C22H16N2O4: C, 70.96; H, 4.33; N, 7.52%. Found: C, 70.93; H, 4.37; N, 7.50%.
N-((Z)-1-oxo-1-(4-chlorophenyl)-3-(3-nitrophenyl)prop-2-en-2-yl)-4-nitrobenzamide (3d). White Solid, m.p. 246-248˚C; 1H NMR (400 MHz, CDCl3): δ 8.54 (br, NH), 8.40-8.38 (m, 3H), 8.23 (d, J = 7.5 Hz, 1H), 8.08 (d, J = 8.6 Hz, 2H), 7.87 (d, J = 8.3 Hz, 2H), 7.77 (d, J = 7.6 Hz, 1H), 7.62-7.54 (m, 3H), 7.08 (s, 1H) ppm; 13C NMR (400MHz, CDCl3): δ 193.4, 163.7, 149.7, 139.4, 137.3, 135.1, 133.1, 132.6, 130.9, 129.1, 128.8, 128.7, 126.2, 124.2, 123.8, 122.3 ppm. Anal.Calcd for C22H14ClN3O6: C, 58.48; H, 3.12; N, 9.30%. Found: C, 58.45; H, 3.16; N, 9.2%.
N-((Z)-1-oxo-1-(4-chlorophenyl)-3-(2,4- dichlorophenyl) prop- 2-en-2-yl)-4-nitrobenzamide (3e): White solid, m.p. 197-199; 1H NMR ( 400 MHz, CDCl3): δ 8.50 (br, NH), 8.19 (dd, J = 8.8, 2.1 Hz, 2H), 7.88 (dd, J = 8.8, 2.1 Hz, 2H), 7.81 (dt, J = 8.6,, 2.1 Hz, 2H), 7.45-7.42 (m, 2H), 7.41 (d, J = 8.7 Hz, 1H), 7.17 (d, J = 8.4, 2.2 Hz, 1H), 6.95 (s, 1H) ppm; 13C NMR (400MHz, CDCl3): δ; 13C NMR (400MHz, CDCl3): δ 191.9, 162.9, 150.1, 139.9, 138.0, 135.8, 134.9, 134.1, 133.2, 131.3, 131.0, 130.0, 129.9, 129.8, 129.0, 128.6, 127.4, 124.0 ppm. Anal.Calcd for C22H13N2O4: C, 55.55; H, 2.75; N, 5.89%. Found: C, 55.53; H, 2.78; N, 5.86%.
N-((Z)-1-oxo-1,3-diphenylprop-2-en-2-yl)-benzamide (3f):
White solid, m.p. 160-162 °C; 1H NMR ( 400 MHz, CDCl3): δ 8.33 (br, NH), 7.88 (dd, J = 8.6, 2.1 Hz, 2H), 7.80 (s, 1H); 7.75 (dd, J = 8.4, 2.1 Hz, 2H), 7.86-7.4 (m, 10H), 7.01 (s, 1H) ppm; 13C NMR (400MHz, CDCl3): δ; 13C NMR (400MHz, CDCl3): δ 192.9, 162.9, 139.7, 138.2, 136.8, 134.9, 133.1, 131.2, 131.0, 130.0, 129.9, 129.8, 129.0, 128.6, 126.8, 124.0 ppm. Anal.Calcd for C22H17NO2: C, 80.71; H, 5.23; N, 4.28%. Found: C, 80.68; H, 5.25; N, 4.27%.
N-((Z)-1-oxo-1-(4-chlorophenyl)-3-(4-chlorophenyl)prop-2-en-2-yl)-4-nitrobenzamide (3g): White solid, m.p. 190-192; 1H NMR ( 400 MHz, CDCl3): δ 8.45 (br, NH), 7.90 (dd, J = 8.6, 2.1 Hz, 2H), 7.85 (dd, J = 8.6, 2.1 Hz, 2H), 7.78 (dt, J = 8.6, 2.1 Hz, 2H), 7.40-7.42 (m, 3H), 7.39 (d, J = 8.4Hz, 1H), 7.15 (d, J = 8.4, 2.2 Hz, 1H), 6.94 (s, 1H) ppm; 13C NMR (400MHz, CDCl3): δ; 13C NMR (400MHz, CDCl3): δ 192.0, 162.8, 150.0, 139.6, 138.1, 135.6, 134.4, 134.0, 133.2, 131.3, 131.0, 129.8, 129.3, 128.4, 127.1, 123.7 ppm. Anal.Calcd for C22H13N2O4: C, 59.88; H, 3.20; N, 6.35%. Found: C, 59.71; H, 3.26; N, 6.32%.
1H NMR N-((Z)-1-oxo-1-phenyl-3-(4-chlorophenyl)prop-2-en-2-yl)-4-nitrobenzamide(3a)
Expanded 1H NMR N-((Z)-1-oxo-1-phenyl-3-(4-chlorophenyl)prop-2-en-2-yl)-4-nitrobenzamide(3a)
13C NMR N-((Z)-1-oxo-1-phenyl-3-(4-chlorophenyl)prop-2-en-2-yl)-4-nitrobenzamide(3a)H NMR N-((Z)-1-oxo-1-phenyl-3-(3-nitrophenyl)prop-2-en-2-yl)-4-nitrobenzamide (3b)
C NMR N-((Z)-1-oxo-1-phenyl-3-(3-nitrophenyl)prop-2-en-2-yl)-4-nitrobenzamide (3b)
H NMR N-((Z)-1-oxo-1-phenyl-3-(phenyl)prop-2-en-2-yl)-4-nitrobenzamide(3c)
C NMR N-((Z)-1-oxo-1-phenyl-3-(phenyl)prop-2-en-2-yl)-4-nitrobenzamide(3c)
HNMR N-((Z)-1-oxo-1-(4-chlorophenyl)-3-(3-nitrophenyl)prop-2-en-2-yl)-4-nitrobenzamide(3d)
C NMR N-((Z)-1-oxo-1-(4-chlorophenyl)-3-(3-nitrophenyl)prop-2-en-2-yl)-4-nitrobenzamide(3d)
HNMR N-((Z)-1-oxo-1-(4-chlorophenyl)-3-(2,4-dichlorophenyl)prop-2-en-2-yl)-4-nitrobenzamide (2e)
CNMR N-((Z)-1-oxo-1-(4-chlorophenyl)-3-(2,4-dichlorophenyl)prop-2-en-2-yl)-4-nitrobenzamide (2e)
N-((Z)-1-oxo-1,3-diphenylprop-2-en-2-yl)-benzamide (2f)
N-((Z)-1-oxo-1,3-diphenylprop-2-en-2-yl)-benzamide (2f)
N-((Z)-1-oxo-1-(4-chlorophenyl)-3-(4-chlorophenyl)prop-2-en-2-yl)-4-nitrobenzamide (3g)