PDF Publication Title:
Text from PDF Page: 007
Molecules 2018, 23, 1436 7 of 13 Organic solvents were evaporated with reduced pressure using Büchi evaporators. Reactions were monitored by TLC using Yantai JingYou (Yantai, China) GF254 silica gel plates. Silica gel column chromatography was performed on an Isolera One system (Biotage, Uppsala, Sweden), and silica gel (200–300 mesh) from Qingdao Hailang Inc. (Qingdao, China). NMR spectra were measured on an Avance III 600 MHz spectrometer (Bruker, Fällanden, Switzerland). Chemical shifts were expressed in δ (ppm) and coupling constants (J) in Hz using solvent signals as internal standards (CDCl3, δH 7.26 ppm and δC 77.2 ppm; CD3OD, δH 3.31 ppm and δC 49.0 ppm; d6-acetone, δH 2.05 ppm and δC 29.8 ppm). ESI-MS were recorded on a 1260–6460 Triple Quad LC/MS (Agilent, Waldbronn, Germany) and HR-ESI-MS data were acquired on an Agilent Q-TOF 6520 system. 3.2. Chemistry 3.2.1. Synthesis of 3-(Naphthalen-1-ylamino)propanoic Acid (2, C13H13NO2) A mixture of naphthalen-1-amine 1 (2.0 g, 14.0 mmol, 1 equiv), 3-bromopropanoic acid (2.1 g, 14.4 mmol, 1 equiv) and Et3N (1.6 g, 14.4 mmol, 1 equiv) in 10 mL EtOH was refluxed overnight. The solvent was then removed under reduced pressure. The crude product was purified by silica gel flash chromatography using CH2Cl2/MeOH (10:1) as eluent to give compound 2 as a white solid (1.0 g, 3.64 mmol, 26% yield). 1H-NMR (CD3OD): δ 7.95 (d, J = 7.9 Hz, 1H), 7.73 (d, J = 7.8 Hz, 1H), 7.41–7.37 (m, 2H), 7.29 (dd, J = 7.6, 8.1 Hz, 1H), 7.17 (d, J = 8.1 Hz, 1H), 6.63 (d, J = 7.6 Hz, 1H), 3.56 (t, J = 6.8 Hz, 2H), 2.74 (t, J = 6.8 Hz, 2H). 13C-NMR (CD3OD): δ 176.3, 144.8, 135.9, 129.3, 127.6, 126.6, 125.4, 125.3, 121.7, 118.2, 105.2, 40.8, 34.4. ESI-MS m/z [M + H]+ calcd for C13H14NO2+ 216.1, found 216.2. 3.2.2. Synthesis of 5-(Diethylamino)-2-nitrosophenol Hydrochloride (4, C10H15ClN2O2) A solution of 3-diethylaminophenol 3 (3.3 g, 20 mmol, 1 equiv) in a mixture of concentrated HCl (7 mL) and water (7 mL) was cooled to 0 ◦C, and then a solution of sodium nitrite (1.4 g, 20 mmol, 1 equiv) in water (10 mL) was added dropwise to the above mixture. The reaction was stirred at 0–5 ◦C for 3.5 h to give a brown slurry. The slurry was filtered and washed with 4M aqueous HCl (6 mL) to give compound 4 as a brown solid (3.0 g, 13 mmol, 65% yield). This compound was used in the next step without further purification. 1H-NMR (CD3Cl): δ 7.37 (d, J = 8.0 Hz, 1H), 6.55 (m, 1H), 5.70 (d, J = 4.2 Hz, 1H), 3.50 (q, J = 8.0 Hz, 4H), 1.29 (t, J = 8.0 Hz, 6H). 13C- NMR (CD3Cl): δ 169.6, 157.4, 149.8, 135.8, 113.6, 96.3, 46.2, 13.5. ESI-MS m/z [M + H]+ calcd for C10H15N2O2+ 195.1, found 195.2. 3.2.3. Synthesis of N-Ethyl-N-(5-(3-methoxy-3-oxopropylamino)-9H-benzo[a]phenoxazin-9-ylidene) ethanaminium Chloride (PS1, C24H26ClN3O3) To a cold (ice bath) solution of 4 (160 mg, 0.6 mmol, 1.2 equiv) in MeOH (10 mL) was added 2 (100 mg, 0.5 mmol, 1 equiv) and 5 drop of concentrated HCl. The mixture was refluxed for 4 h. The solution was evaporated and purified by flash chromatography using CH2Cl2/MeOH (10:1) as eluent to give PS1 as a blue solid (45 mg, 0.12 mmol, 24% yield). 1H-NMR (CD3OD): δ 8.83–8.80 (m, 1H), 8.29 (d, J = 8.0 Hz, 1H), 7.88 (dd, J = 7.2, 8.0 Hz, 1H), 7.81 (dd, J = 5.0, 9.3 Hz, 1H), 7.77 (dd, J = 7.2, 8.2 Hz, 1H), 7.28 (d, J = 9.3 Hz, 1H), 6.96 (s, 1H), 6.89 (s, 1H), 3.99 (t, J = 6.7 Hz, 2H), 3.75 (s, 3H), 3.71 (q, J = 7.2 Hz, 4H), 2.96 (t, J = 6.7 Hz, 2H), 1.35 (t, J = 7.2 Hz, 6H). 13C-NMR (CD3OD): δ 173.2, 159.1, 155.9, 153.1, 149.9, 134.7, 134.2, 132.9, 132.6, 132.1, 130.8, 125.2, 124.7, 123.8, 117.0, 97.0, 94.4, 52.5, 47.1, 41.4, 33.6, 13.0. ESI-MS m/z [M]+ 404.3. HR-ESIMS: [M]+ calcd for C24H26N3O3+ 404.1969, found 404.1967. 3.2.4. Synthesis of N-(2-Morpholinoethyl)-3-(naphthalen-1-ylamino)propanamide (5, C19H25N3O2) Compound 2 (100 mg, 0.5 mmol, 1 equiv) was dissolved in CH2Cl2 (10 mL), and then 2-morpholinoethanamine (120 mg, 0.9 mmol, 1.8 equiv), HATU (200 mg, 0.5 mmol, 1 equiv) and iPrNEt2 (0.2 mL, 1 mmol, 2 equiv) was added. The mixture was stirred overnight, and then concentrated. The residue was purified by silica gel chromatography with petroleum ether/acetone (1:1) as eluent to give compound 5 as a white solid (128 mg, 0.42 mmol, 84% yield). 1H-NMR (CDCl3): δ 7.83 (d,PDF Image | Photosensitizers for Anticancer Photodynamic Therapy
PDF Search Title:
Photosensitizers for Anticancer Photodynamic TherapyOriginal File Name Searched:
molecules-23-01436-v2.pdfDIY PDF Search: Google It | Yahoo | Bing
Cruise Ship Reviews | Luxury Resort | Jet | Yacht | and Travel Tech More Info
Cruising Review Topics and Articles More Info
Software based on Filemaker for the travel industry More Info
The Burgenstock Resort: Reviews on CruisingReview website... More Info
Resort Reviews: World Class resorts... More Info
The Riffelalp Resort: Reviews on CruisingReview website... More Info
| CONTACT TEL: 608-238-6001 Email: greg@cruisingreview.com | RSS | AMP |