4-(4-Chlorophenyl)-2-thiazolamine

white to light yellow crystal powde

General procedure: A mixture of thiourea (1.2 mmol) and 2-bromoacetophenone (1 mmol) in EtOH (2 mL) was stirred at 70 oC for 1h. The reaction mixture was cooled to room temperature, poured into ice-cold water, and the resulting precipitate was filtered and dried to give the desired compounds: [6a ( 99percent) as a white solid, mp 150-152 oC (Lit.26 149-150 oC) ; 6b (100percent) as a white solid, mp 162-165 oC (Lit.26 163-164 oC); 6c (0.236 g, 93percent) as a white solid, mp 179-181 oC (Lit.26 180-181 oC); 6d (98percent) as a white solid, mp 203.6-204.2 oC (Lit.28/22 204.0-204.5 oC); 6e (94percent) as a bright yellow solid, mp 287-288 oC (Lit.26, 27 285-286 oC); 6f (100percent) as a white solid, mp 172-174 oC (Lit.29-31 172 oC).General procedure: The appropriate phenacylbromide or 3-(2-bromoacetyl)-2H-chromen-2-one (1mmol) and either thiourea, phenylthiourea or selenourea (1mmol) were dissolved in 2mL of methanol, water (2mL) containing 0.02g of NaF added and the mixture stirred at room temperature for the appropriate time. After completion of the reaction, 10mL of water was added and the solid that separated out was filtered off and washed with water, affording analytically pure substituted 1, 3-thiazoles or 1, 3-selenazole derivatives in excellent yields.General procedure: A 100-mL borosil test-tube was charged with phenacyl bromide (1a–h)/3(2-bromoacetyl)coumarin (1i–n) (1 mmol), thiourea (2a)/phenylthiourea (2b)/selenourea(2c) (1 mmol) and water (1 mL). The tube was kept in such a way that thesurface of the reactants is just lower than the water level of the ultrasonic bath inwhich they were sonicated with a frequency of 50 kHz at 25 C for about 10–60 s.The progress of the reaction was monitored by TLC. After completion of thereaction, the solid separated out was filtered and washed with water. Analyticallypure products were obtained without further recrystallization.A mixture of thiourea (1.0 eq.), the α-haloketone (1.2 eq.) and dry ethanol (1 mL per 100 mg ofthiourea) was heated at reflux until the disappearance of the thiourea (12 h, checked by TLC, SiO2, petroleum ether:EtOAc 70:30). After that, the mixture was cooled at room temperature, and theprecipitated was filtered off and washed with ethanol:water (80:20). The solid was recrystallizedfrom ethanol or ethanol:water. Yield: 98percent; white solid, m.p. 167–168 °C; 1H NMR (400 MHz, CDCl3)δ: 7.74–7.70 (m, 2H), 7.38–7.33 (m, 2H), 6.73 (s, 1H), 5.07 (bs, 2H); 13C NMR (100 MHz, CDCl3) δ:167.3, 150.2, 133.4, 133.1, 128.8, 127.3, 103.3. MS (EI) m/z (abundance, percent): 211.01 (M+, 100). Anal. calc.for C9H9ClN2S: C, 51.06percent; H, 3.81percent; Cl, 16.75percent; N, 13.23percent; S, 15.15percent; found: C, 51.0percent; H, 3.8percent; Cl, 16.8percent; N, 13.2percent; S, General procedure: α-Bromoarylethanones (deliquescent) were prepared accordingto the reported method [18]. The ethanolic mixture of α-bromoarylethanone (1a, 1 mmol) and thiourea in the boiling tube was ultrasonicated at 45 °C in an ultrasonic bath. The reaction was monitored by TLC at every 5 min. It was found that the heterocyclization was completed within 20 min. The same procedure was followed for the synthesis of 2-amino-4-substituted phenyl-1, 3-thiazoles listed in Table 1General procedure: 4.5. Microwave-assisted synthesis of substituted 4-phenylthiazol-2-amines (15e18) via Hantzsch condensationIn a sealed tube, a stirred solution of thiourea (10.91 mmol) andthe appropriate a-bromoacetophenone (10.91 mmol) in ethanol(15 mL) was irradiated (800 W) at 100 C for 15 min. The solventwas evaporated to dryness. The solid residue was neutralized witha saturated solution of sodium bicarbonate and extracted threetimes with methylene chloride. The organic layer was dried overmagnesium sulfate and the solvent was evaporated to dryness. Thesolid residuewas agitated for 30 min in cyclohexane and filtered offto afford the 4-phenylthiazol-2-amine in analytically pure form.Method xxi-Step 1: A mixture of 2-bromo-l-(4-chlorophenyl)ethanone (1 g, 4.28 mmol) and thiourea (0.326 g, 4.28 mmol) were placed in a MW test tube containing a magnetic stirring bar, rubber cap, and EtOH (Volume: 15 ml). The test tube was placed in the microwave cavity and subjected to MW irradiation at 50 oC (100 W) for 5 min. After completion of the reaction, the tube was removed, cooled to room temperature, and the contents added to water (10 mL). The product was extracted into methylene chloride (15 mL), which was filtered though a short silica column to afford the 2-aminothiazole (90percent yield); LCMS: m/z (M+H)General procedure: Substituted phenacylbromide (0.01 mol) and thiourea (0.76 g, 0.01 mol) were takenin a reaction vessel and added water (10 mL). The reactionmixture was irradiated under micro wave (40 W) for 10-15min. The solid separated was filtered, washed with water andrecrystallized from absolute alcohol [17, 23].Compound 2a (R = Cl): White solid; Yield 78.70 percent; m.p.188 °C; R f 0.80; λ max 238 nm; IR (KBr, ν max , cm -1 ): 3360.20(1 NH 2 , str.), 3063.22 (Ar-CH, str), 1686.10 (Ar C=C), 1602.45(NH 2 bend), 1534.30 (CN str.), 770.60 (C-S), 687.10 (C-Cl).General procedure: Different substituded acetophenone (10a–10c, 10e–10h) (10 mmol), iodine (1.0 equiv.) and thiourea(2.0 equiv.) were dissolved in DMF, then the mixture heated at 100 oC overnight with stirring. WhenTLC indicated that the reaction was complete, the mixture was cooled and diethyl ether added toremove un-reacted iodine and corresponding acetophenone. The solid residue was then put in distilledwater and treated with saturated sodium sulfite solution and the solid that separated was filtered, washed and dried under reduced pressure to afford product 12a–12g. 5A visible light driving method for synthesizing 4-alkyl or aryl-2-aminothiazoles. This method refers to adding olefin azide compound, ammonium thiocyanate and copper acetate to solvent acetonitrile, respectively, driving at a temperature of 25° C. under visible light with a wavelength of 455 nm, and obtaining a reaction solution after 28 h. The reaction solution was spin-dried at a temperature of 25° C. and a pressure of 1.3 kPa to obtain a concentrate; the concentrate was subjected to silica gel column chromatography (200 to 300 mesh silica gel, eluent: petroleum ether: ethyl acetate=6 mL: 1 mL) gives 4-(4-chlorophenyl)-2-aminothiazole (2c) as a white solid (20 mg, 95percent).Add 3 mL of water in a 25 mL reaction flask. 30 μL Tween, 0.50 mmol 1-chloro-4-ethylbenzene, 1.50mmol NBS and 0.05mmol AIBN, reacted at 60 ° C for 4h, After the reaction is finished, it is cooled. Then, 1.50 mmol of sodium hydrogencarbonate and 0.50 mmol of thiourea were added in sequence, and the reaction was carried out at 80 ° C for 1 h. After the reaction was completed, ethyl acetate was added and extracted with saturated brine. Concentrated organic phase, Column chromatography gave 97 mg of a white solid. The yield was 92percent.Add 3 mL of water to a 25 mL reaction flask, and then add 0.50 mmol of 1-chloro-4-ethylbenzene and 0.75 mmol of DBH.And 0.05mmol TBHP, reacted at 60 ° C for 4h, after cooling, then add 1.50mmol potassium carbonate and 0.50mmol thiourea, The reaction was continued at 80 ° C for 1 h. After the reaction was completed, ethyl acetate was added for extraction, and the organic phase was concentrated and purified by column chromatography.95mg white solid, The yield was 90percent.General procedure: A mixture of methyl carbonyl (2 mmol), thiourea (3 mmol), NIS(2 mmol), and NH2-MMT (0.10 g) in EtOH (5 mL) at room temperature was stirred until completion of reaction. The progress of the reaction was monitored by TLC (petroleum ether-ethyl acetate 4:1). After completion of the reaction, the NH2-MMT was separated by filtration. After evaporation of EtOH under vacuum, the crude product was dissolved in boiling water and adjusted to pH 8 withthe amount of ammonia to give the solid products. The solid obtained was recrystallized from a mixture of ethanol-water.General procedure: A mixture of the acetophenone (2 mmol), thiourea (3 mmol) and iodine (2 mmol), in the presence of 0.03 g nanochitosan was refluxed in EtOH. General procedure: Method A: A mixture of p-substituted acetophenone 1 (8.6 mmol), thiourea 2 (17.2 mmol, 1.3 g) and iodine (8.6 mmol, 2.2 g) was placed in an open vessel containing a Teflon coated stir bar. The vessel was placed in the microwave cavity (CEM, Discover) and subjected to MW irradiation (50 W) at indicated temperature for 10 min. After the completion of the reaction, the crude mixture was cooled to 70 °C and then it was triturated, filtered and washed with EtGeneral procedure: A mixture of methylcarbonyl (0.5 mmol), thiourea (0.5 mmol), iodine (0.5 mmol), DMSO (2 mL) and 20 mg MMT-K10 was stirred at 80 °C. After completion of the reaction (monitored by TLC, petroleum:ethyl acetate, 4:1), the catalyst was separated by filtration, and then the solvent was removed under reduced pressure. The crude product was dissolved in hot water, extracted with ether (3 9 30 mL), and adjusted to pH = 9–10 by ammonia to give the solid products. Finally, the resulting precipitate was recrystallyzed by EtOH.General procedure: A mixture of methylcarbonyl (0.5 mmol), thiourea(0.5 mmol), iodine (0.5 mmol), DMSO (2 mL) and 10 mgStarch NPs were stirred at 80 C. After completion of thereaction (monitored by TLC, petroleum:ethyl acetate, 4:1), the reaction was quenched by the addition of 10 mL distilledwater. The aqueous solution was extracted withEtOAc (3 9 10 mL) and the combined extract was driedwith anhydrous Na2SO4. The solvent was vacuumed, andfinally, the resulting precipitate was recrystallized byEtOH.General procedure: 2-Amino-4-phenyl thiazoles (7General procedure: A mixture of thiourea (50 mmol), the corresponding acetophenone (25 mmol) and iodine (25 mmol) is stirred at 100 °C for 8 h.Then the reaction mixture is cooled, extracted with diethyl ether toremove excess of acetophenone, and then washed with aqueous sodium thiosulfate to remove excess iodine and later with cold water. The crude product is dissolved in hot water, filtered to remove sulphone, and the filtrate is basified with aqueous Na2CO3to yield the corresponding 2-amino-4-(substituted-phenyl)-1, 3-thiazole. The crude product is purified by recrystallization from alcohol.General procedure: Thiourea (0.2 mol) and iodine (0.2 mol)were triturated and mixed with acetophenone/itsderivatives (0.1 mol). The mixture was heated on a waterbath, with constant shaking, for 8 h. The solid obtainedwas triturated with diethyl ether to remove unreactedacetophenone. Excess of ether was distilled off. Thecrude product was dissolved in hot water and fi ltered toremove sulphone formed during the course of reaction.The product was precipitated by adding ammonia solutionto the fi ltrate. The precipitates were washed with waterand crystallized from methanol to obtain 4-phenylthiazol-2-amine and its derivatives 4-6 [23, 24].2-Thiocyanato-1- (4-chlorophenyl) ethanone was added to the reaction flask0.422 g (2.0 mmol), 0.231 g (3.0 mmol) of ammonium acetate, 5 ml of toluene, The reaction solution was reacted at 80 ° C.TLC followed the reaction until complete;The crude product obtained after the end of the reaction was separated by column chromatography (petroleum ether: ethyl acetate = 10: 1)To give the object product (yield 81percent).In a 25 mL reaction flask, add 3 mL of water and 30 μL of Tween, 0.5 mmol of chlorostyrene and 0.75 mmol of DBH reacted at 60 °C for 1 h.After the reaction was completed, the water was swirled, 3 mL of ethanol was added, and 0.75 mmol of thiourea was added. The reaction was refluxed for 1 h. After the reaction was completed, ethanol was spin-dried.Ethyl acetate was added to dissolve, and saturated saline solution was added for extraction.The organic phase was concentrated and column chromatography gave 94 mg of a white solid with a yield of 89percent.

Molecular Weight:210.68
XLogP3:3.2
Hydrogen Bond Donor Count:1
Hydrogen Bond Acceptor Count:3
Rotatable Bond Count:1
Exact Mass:210.0018471
Monoisotopic Mass:210.0018471
Topological Polar Surface Area:67.2
Heavy Atom Count:13
Complexity:171
Covalently-Bonded Unit Count:1
Compound Is Canonicalized:Yes