Synthesis of Indolo and benzimidazoquinazolines and benzodiazepines

Duncan, Robert L.; Helsley, Grover C.; Boswell, Robert F.

doi:10.1002/jhet.5570100115

Cited by 12 publications

(5 citation statements)

References 4 publications

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“…1 H NMR (400 MHz, CDCl3)  = 8.92 (br s, 1H, NH), 7.72 (dd, J = 8.2, 1.1 Hz, 1H, H6), 7.62-7.52 (m, 2H, H8 and H9), 7.35 (ddd, 1H, J = 7.9, 7.3, 1.3 Hz, H7), 6.94-6.92 (m, 1H, H1), 6.49-6.47 (m, 1H, H3), 6.32 (td, J = 6.2, 2.6 Hz, 1H, H2); 13 C NMR (101 MHz, CDCl3) C =148. 1, 132.4, 130.8, 127.1, 127.0, 126.3, 124.4, 120.5, 111.0, 110.1; FTIR (neat)cm -1 = 3414, 3106, 1607, 1517, 1481, 1344, 1285, 1115, 1088, 1037; LRMS (ESI -) 187 ([M -H] -).…”

Section: S6mentioning

confidence: 99%

Section: S6mentioning

confidence: 99%

“…The data matched that previously reported in the literature. 7 Melting point 98-100 o C (ethanol) [lit. 104-106 o C]; 7 1 H NMR (400 MHz, CDCl3)  = 7.42-7.38 (m, 1H, H8), 7.37-7.31 (m, 2H, H2), 7.28 (br s, 1H, NH hydrazine), 7.17-7.09 (m, 3H, H3 and H10), 6.95 (tt, J = 7.4, 1.1 Hz, 1H, H1), 6.81-6.76 (m, 2H, H9 and H11), 5.86 (br s, 2H, NH2 aniline), 2.33 (s, 3H, H6);…”

Section: -(1-(2-phenylhydrazono)ethyl)aniline 43mentioning

confidence: 99%

“…The filtrate was concentrated under reduced pressure. Purification of the residue via column chromatography eluting with 1:19 diethyl ether/petrol 40-60 afforded the title compound 35 as a yellow oil (203 mg, 42%).1 H NMR (500 MHz, CDCl3)  = 9.58 (br s, 1H, NH), 7.72 (dd, J = 7.9, 1.3 Hz, 1H, H6),7.24 (td, J = 7.6, 1.4 Hz, 1H, H7), 7.18 (td, J = 7.6, 1.3 Hz, 1H, H8), 6.89-6.87 (m, 1H, H1),6.71 (dd, J = 7.9, 1.3 Hz, 1H, H9), 6.62-6.59 (m, 1H, H3), 6.27 (dd, J = 6.1, 2.7 Hz, 1H, H2), 2.10 (s, 3H, H13); 13 C NMR (126 MHz, CDCl3) C = 158.0 (q, J = 33.7 Hz), 142.0, 130.3, 127.6, 127.1, 126.5, 125.1, 120.2 (q, J = 278.5 Hz), 119.9, 119.6, 109.5, 108.0, 15.3; NMR (470 MHz, CDCl3) F = -74.1 (s); FTIR (neat)cm -1 = 3412 (br), 1683, 1596, 1484, 1433, 1333, 1220, 1186, 1137, 1113, 1038; HRMS (ESI + ) calculated for C13H12F3N2 = 253.0947, mass found = 253.0956; By-product 44 was isolated as a yellow oil (334 mg, 48 %): 1 H NMR (500 MHz, CDCl3)  = 9.87 (br s, 1H, NH), 7.69 (dd, J = 7.6, 1.6 Hz, 1H, H6), 7.24 (td, J = 7.5, 1.5 Hz, 1H, H7), 7.20 (td, J = 7.5, 1.5 Hz, 1H, H8), 6.71 (dd, J = 7.7, 1.4 Hz, 1H, H9), 6.54 (dd, J = 3.8, 2.8 Hz, 1H, H2/3), 6.26 (t, J = 3.2 Hz, 1H, H2/3), 2.44 (s, 1H, OH), 2.11 (s, 3H, H13), 1.77 (s, 3H. H16); 13 C NMR (126 MHz, CDCl3) C = 157.8 (q, J = 33.9 Hz), 141.6 , 130.5, 129.7, 127.2, 126.7, 126.3, 125.1 (q, J = 284.8 Hz), 124.1, 119.7 (q, J = 278.4 Hz), 119.6, 107.8, 107.7, 72.1 (q, J = 30.6 Hz), 22.5, 14.9; 19 F NMR (470 MHz, CDCl3) F = -74.4 (s), -81.8 (s); FTIR (neat)cm -1 = 3400 (br), 1683, 1504, 1461, 1335, 1221, 1138, 1113, 1055; HRMS (ESI + ) calculated for C16H14F6N2NaO = 387.0903, mass found = 387.0895; Imine 35 (100 mg, 0.40 mmol) was dissolved in toluene (4.0 mL) and N-benzylcinchoninium chloride (17 mg, 0.040 mmol) was added.…”

mentioning

confidence: 99%

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Cation-Directed Enantioselective N-Functionalization of Pyrroles

Armstrong

D’Ascenzio

Smith

2015

Synlett

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Supporting Information Reactions requiring moisture-sensitive reagents were carried out in oven dried glassware, under an atmosphere of nitrogen (balloon pressure). Dichloromethane, diethyl ether, toluene and methanol were purified by filtration through activated alumina columns employing the method of Grubbs et al. 1 Water was purified by an Elix ® UV-10 system. Reagents were used directly as supplied by major chemical suppliers, or following purification procedures described by Perrin and Armarego. 2 Petrol 40-60 refers to the fraction of petroleum ether which boils in the range 40-60 o C. Brine refers to a saturated aqueous solution of sodium chloride. Column chromatography was carried out using Merck Geduran ® Silicagel (40-63 m particle size). Analytical thin layer chromatography was carried out using pre-coated, aluminium backed plates (Merck Kieselgel 60 F254). Visualisation was achieved with ultraviolet irradiation (254 nm) and staining with vanillin. NMR spectroscopy was carried out using Bruker Avance spectrometers in the deuterated solvent stated, using the residual non-deuterated solvent signal as an internal reference. Chemical shifts are quoted in ppm, based on appearance rather than interpretation. Infrared spectra samples were prepared as a neat film and were recorded using a Bruker Tensor 27 FTIR spectrometer using an ATR module. Low resolution mass spectroscopy was carried out using ESI and was performed on a Micromass LCT Premier spectrometer. HRMS was carried out using Bruker MicroTOF and Micromass GCT spectrometers under ESI or FI conditions respectively. Analytical chiral HPLC was carried out using a Dionex Ultimate 3000 HPLC system comprising a Dionex LPG-3400A pump, WPS-3000SL autosampler and TCC-3000SD column compartment, and a Daicel Chiralpak column (0.46 cm x 25 cm), equipped with an appropriate guard column (0.4 cm x 1 cm). Melting points were determined using a Reichert melting point apparatus and are uncorrected. Optical rotations were recorded on a Perkin-Elmer 241 polarimeter. Concentrations are quoted in g/100 mL. S3 1.2 General Experimental Procedures General Procedure A: Imine Formation/Asymmetric Cyclization Imine Formation: A slurry of pyrroloaniline 1, the appropriate aldehyde and oven dried anhydrous magnesium sulfate in anhydrous toluene was stirred at room temperature for 16 hours and then filtered through a plug of Celite ® washing with anhydrous diethyl ether. The filtrate was concentrated under reduced pressure. Cyclization: The crude imine thus obtained was dissolved in toluene and N-benzylcinchoninium chloride was added. The resulting stirred suspension was cooled to the appropriate temperature and aqueous potassium hydroxide precooled to the appropriate temperature was added. The biphasic reaction mixture was rapidly stirred at the appropriate temperature for the appropriate time. After this time, water was added and the solution was allowed to warm to room temperature. The organic layer was separated and the aqueous layer was extracted three times with dichloromet...

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Section: S6mentioning

confidence: 99%

Section: S6mentioning

confidence: 99%

Section: -(1-(2-phenylhydrazono)ethyl)aniline 43mentioning

confidence: 99%

mentioning

confidence: 99%

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Cation-Directed Enantioselective N-Functionalization of Pyrroles

Armstrong

D’Ascenzio

Smith

2015

Synlett

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“…Hendi et al reported 2,3,4,5-tetrahydro-1H-1,4-diazepinoindoles as serotonin antagonists (50). Duncan and coworkers investigated some novel ring systems which resulted in benzodiazepine type structures (52) for CNS activity [83]. Brzechffa et al found the benefit of indolodiazepines as starting material to synthesize new analogs of diaza heterocycles (51) via -elimination reaction [82].…”

Section: Indolodiazepinesmentioning

confidence: 99%