* All experimental methods are cited from the reference, please refer to the original source for details. We do not guarantee the accuracy of the content in the reference.
With water; caesium carbonate; for 0.166667h;Microwave irradiation;
General procedure: Add 2 ml of water to the microwave reactor,1 mmol of benzothioamide and 0.2 mmol of cesium carbonate,Reacted at a fixed power of 120 W for 10 min,Extracted with ethyl acetate and concentrated under reduced pressure.To give a pale yellow solid, yield 99%.
87%
With potassium thioacyanate; sodium hydroxide; In water; at 100.0℃; for 0.5h;Microwave irradiation;
General procedure: In the reaction vessel, 2-iodoaniline (1 mmol), 4-methylbenzaldehyde (1 mmol), potassium thiocyanate (2.4 mmol), nickel/proline lithium complex (0.05 mmol), sodium hydroxide (1 mmol), and water (3 mL) were added.After being placed under the microwave reactor,Set in a microwave reactor to 100 C was heated for 30 minutes at 150 W power, cooled to room temperature.The product was extracted with ethyl acetate and concentrated under reduced pressure. The product was purified by column chromatography to give a white solid in 93% yield.
78%
With acetic acid; at 20.0℃; for 0.333333h;
General procedure: Add 1 ml of catalytic amount of glacial acetic acid to the mortar.1 mmol of o-aminophenol,1.2 mmol of benzaldehyde was rapidly ground at room temperature for 20 minutes.The product was extracted with ethyl acetate and water.Reduced pressure,The product was purified by column chromatography to give a pale yellow solid.The yield was 88%.
2
[ 3132-99-8 ]
[ 137-07-5 ]
[ 19654-14-9 ]
Yield
Reaction Conditions
Operation in experiment
91%
With air; In ethyl acetate; at 20.0℃;Irradiation;
General procedure: To a 20 mL glass tube with a stir bar was charged 2-aminothiophenol 1a (50 mg, 0.4 mmol), benzaldehyde 2a (51 mg, 0.48 mmol) and EtOAc (2 mL). The solution was stirred at room temperature with the irradiation of a 12 W blue LED for 6 h. The solvent was removed under vacuum. The residue was purified by column chromatography over silica gel (petroleum ether/ethyl acetate = 40/1) to give the product 3a (77 mg, 91%).
89%
With cerium(IV) oxide; In water; at 25.0℃; for 0.333333h;
General procedure: Amixture of 2-aminothiophenol (1 mmol) and benzaldehyde (1 mmol) wasstirred in presence of Nano CeO2 (5 mol %) in water at roomtemperature for 20 minutes. After completion, the reaction mixture was dilutedwith ethyl acetate and subsequently centrifuged to get the catalyst. Further thereaction mixture was extracted with ethyl acetate (10 x 3mL) and dried over Na2SO4. The solvent was evaporated under reducedpressure to obtain product. The crude product was purified on silica gel columnby using pet ether and ethyl acetate as solvent to get the pure product
57%
With potassium carbonate; 1-methyl-3-(n-butyl)imidazolium iodide; In o-xylene; para-xylene; m-xylene; at 120.0℃; for 10.0h;Green chemistry;
General procedure: Into a 15x150 mm glass tube were layered o-amino phenol (1a-1d)/benzenethiol (4) (1 mmol) and corresponding aldehyde (1 mmol), xylene (3 mL; mixture of o, m, p-xylene), 0.25 mmol K2CO3 (34 mg) and NHC precursor G (0.1 mmol, 26 mg), the mixture was lowered under pre-heated oil bath, the mixture was stirred vigorously for 10 hours under air atmosphere. After reaction, the mixture was diluted with ethyl acetate, filtrated, the organic solution was concentrated under vacuum, the residue was applied on silica gel column chromatography, which afforded the corresponding oxidative cyclization product 3aa-3dd; 5a-5n.
With sodium carbonate;tetrakis(triphenylphosphine) palladium(0); In tetrahydrofuran; water; at 80℃;Inert atmosphere;
A mixture of <strong>[365564-05-2]1,3,5-tris(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)benzene</strong> (4) (500 mg, 1.14 mmol), 2-(3-bromophenyl)benzo[d]thiazole (7) (1.15 g, 3.98 mmol), tetrakis(triphenylphosphine)palladium (140 mg, 0.12 mmol), sodium carbonate (1.51 g, 14.2 mmol), THF (25 mL), and water (14 mL) was degassed for 25 minutes. The mixture was heated at reflux (80 C.) overnight under argon. After cooling, the mixture was poured into ethyl acetate (125 mL) then washed with saturated sodium bicarbonate solution (100 mL), water (100 mL), and brine (100 mL). A flash column (gradient of 5 to 10% acetone in hexanes) and precipitation from methylene chloride/methanol gave 611 mg of material (ET-3) in 76% yield.
In water; N,N-dimethyl-formamide; for 3.0h;Sonographic reaction;
2-Aminothiophenol (5.0 g, 39.9 mmol) and 3-bromobenzaldehyde (7.39 g, 39.9 mmol) was dissolved in anhydrous DMF. Trimethylsilylchloride (10.84 g, 99.8 mmol) was added dropwise. The resulting solution was heated at 90 C. overnight under argon. After cooling to room temperature, the mixture was poured into water (100 mL). Mixture was then sonicated in open air for 3 hours, poured into water (200 mL), and extracted with methylene chloride (2×200 mL). Organic washes were combined, washed with brine (200 mL), and dried over sodium sulfate. Flash column (gradient of 3 to 9% ethyl acetate in hexanes) and additional silica plug (5% ethyl acetate in hexanes) gave 4.09 g of material 7 in 35% yield.
With pyridine; potassium tert-butylate; iodine; at 90.0℃; for 2.0h;
General procedure: 18. To a mixture of benzal bromide 1a (25 g, 100 mmol) and 2-aminobenzenethiol 2a (13.75 g, 110 mmol) in pyridine (100 mL) was added t-BuOK (6.25 g, 500 mmol) followed by the addition of iodine (2.62 g, 20 mmol) and the reaction mixture was refluxed at 90 C for 2 h. The completion of the reaction was confirmed by TLC. The black reaction mixture was concentrated and the residue obtained was dissolved in water, and then extracted with ethyl acetate (2 × 500 mL), the combined organic phase was washed with water and brine solution, and dried over anhydrous sodium sulfate. The organic phase was evaporated and the crude product was purified by column chromatography (10% EtOAc/hexanes) to afford the title compound 3a (19.5 g, 92%) as a white solid.
With sodium hydrogen sulfide; at 190.0℃; for 0.333333h;Microwave irradiation; Green chemistry;
General procedure: 2,2-Disulfanediyldianiline (1a) or 5,5-dichloro-2,2-dithiobisaniline (1b) (0.50 mmol), the corresponding aldehydes(2a-p) (1.1 mmol), NaSH (0.3 mmol) and PEG-300 (2 mL) wereput into a round-bottomed ask, and the reaction mixture wasirradiated for 20 min at 25 W. After completion of the reactionmonitored by TLC with a mixture of petroleum ether and ethylacetate as eluent, the mixture was allowed to cool to roomtemperature. Distilled water (25 mL) was added into the ask,and then the solid was precipitated from the aqueous phaseafter stirring by magnetic stirrers in 5 min. The solid precipitatewas isolated by fltration, washed twice by distilled water (5 mL)and dried for 3 h. The pure targetproducts3a-3o were obtaineddirectly. The pure products 3p and 3q were obtained by columnchromatography(PE/EtOAc as eluent).Complete characterization of the products (all known) is found in the SupplementalMaterials (Figures S 1-S 34).
With [bis(acetoxy)iodo]benzene; palladium diacetate; acetic acid; at 110.0℃; for 4.5h;
General procedure: An oven-dried flask was charged with Pd(OAc)2 (0.05 mmol), diacetoxyiodobenzene (DIB) (1.0 mmol), substituted 2-phenylbenzo[d]thiazole (1-18) (1.0 mmol), and acetic acid (2 mL). Then the reaction vessel was kept in an oil bath preheated to 110 C and allowed to stir for the stipulated period of time. The progress of the reaction was monitored by TLC. During this period complete disappearance of substituted 2-phenylbenzo[d]thiazole was observed with the appearance of one major product having higher Rf [in some cases (1b, 4b, 16b, 15c, 18c)] another product was also observed having lower Rf with respect to the substrate. The reaction mixture was then cooled and admixed with water (5 mL). The product was extracted with ethyl acetate (2×10 mL) and the combined organic layer was washed with saturated sodium bicarbonate (NaHCO3) solution. Organic layer was dried over anhydrous sodium sulfate (Na2SO4) and evaporated under reduced pressure. The crude product so obtained was further purified through silica gel column chromatography (EtOAc/hexane) to yield the pure product. The identity and purity of the products were confirmed by spectroscopic analysis.
diethyl 2-(2-(benzo[d]thiazol-2-yl)-4-bromophenyl)malonate[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
30%
With silver hexafluoroantimonate; dichloro(pentamethylcyclopentadienyl)rhodium (III) dimer; In 1,2-dichloro-ethane; at 60.0℃; for 20.0h;Sealed tube;
General procedure: To an oven-dried sealed tube charged with 2-(naphthalen-2-yl)benzo[d]thiazole (1a) (52.3 mg, 0.2 mmol, 100 mol %), [RhCp*Cl2]2 (3.1 mg, 0.005 mmol, 2.5 mol %) and AgSbF6 (6.9 mg, 0.02 mmol, 10 mol %) in DCE (1 mL) was added diethyl 2-diazomalonate (2a) (44.7mg, 0.24 mmol, 120 mol %). The reaction mixture was allowed to stir at 60 C for 20 h and cooled to room temperature. The reaction mixture was diluted with EtOAc (3 mL) and concentrated in vacuo. The residue was purified by flash column chromatography (silica gel, nhexanes/EtOAc = 10:1) to afford 78.3 mg of 3a in 93% yield.
2-(2-allyl-5-bromophenyl)benzo[d]thiazole[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
76%
With silver hexafluoroantimonate; dichloro(pentamethylcyclopentadienyl)rhodium (III) dimer; copper diacetate; In tetrahydrofuran; at 20.0℃; for 20.0h;Sealed tube;
General procedure: To an oven-dried sealed tube charged with 2-m-tolylbenzo[d]thiazole (1a) (67.6mg, 0.3mmol, 100mol%), [RhCp Cl2]2 (4.6mg, 0.0075mmol, 2.5mol%), AgSbF6 (10.3mg, 0.03mmol, 10mol%) and Cu(OAc)2 (27.2mg, 0.15mmol, 50mol%) in THF (1mL) was added allyl diethyl phosphate (2c) (116.5mg, 0.6mmol, 200mol%). The reaction mixture was allowed to stir at room temperature for 20h. The reaction mixture was diluted with EtOAc (3mL) and concentrated in vacuo. The residue was purified by flash column chromatography (silica gel, n-hexanes/EtOAc=100:1) to afford 73.4mg of 3a in 92% yield
With copper(II) acetate monohydrate; sodium carbonate; sulfur; In dimethyl sulfoxide; at 130.0℃; for 24.0h;Schlenk technique; Inert atmosphere;
General procedure: 2-Iodoaniline 1a (0.5 mmol), benzyl chloride 2a (1 mmol, 126 mg), sulfur powder (2 mmol, 64 mg), Cu(OAc)2·H2O (20 mg) and Na2CO3 (1 mmol, 106 mg) in DMSO (3 mL) were put into a Schlenk tube. The reaction mixture was stirred at 130 C for 24 h and cooled to room temperature, filtered and extracted with ethyl acetate, washed with brine, dried over Na2SO4, filtered and concentrated. The residue was purified by chromatography on silica gel (300-400 mesh) to afford desired product 3aa as a light yellow solid; yield : 102 mg (97%);
With tetrakis(triphenylphosphine) palladium(0); potassium carbonate; In ethanol; toluene; for 12.0h;Reflux;
A mixture of 2.5 g (4.5 mmol) of Intermediate 4, 1.31 g (4.5 mmol) of Int.6, 0.16 g (0.14 mmol) of Pd (PPh3) 4, 5 mL (10 mmol) of 2M K2CO3, 13 mL of toluene and 5 mL of ethanol was refluxed for 12 hours. The reaction mixture was cooled to room temperature and the resulting precipitate was filtered under reduced pressure and washed with toluene, water and methanol.The filtered precipitate was dried under reduced pressure and recrystallized from dichloromethane and methanol to obtain 1.21 g (yield: 42%) of solid compound 4-21 (WS16-30-036).
With potassium phosphate; tetrakis(triphenylphosphine) palladium(0); In ethanol; water; toluene;Reflux;
In a one-neck 250 mL flask Int.3 1.85 g (6.36 mmol), Intermediate 5 (3.00 g, 6.36 mmol), 0.37 g (0.32 mmol) of Pd (PPh3) 4, 40 mL of toluene, EtOH 10 mL, 10 mL of H2O and 4.05 g (19.1 mmol) of K3PO4 were mixed, It was refluxed. After the reaction was completed, the reaction mixture was cooled at room temperature and the resulting solid was filtered with EtOH. The solid was dissolved in chloroform and purified by silica gel column chromatography (CHCl3). Solidification with dichloromethane (DCM) and filtration gave 1.7 g (yield: 47.6%) of compound 4-43 (WS16-30-185) as a white solid.
With tetrakis(triphenylphosphine) palladium(0); potassium carbonate; In ethanol; toluene;Reflux;
In a two-neck 250 mL flask, 2.5 g (5.12 mmol) of Int.3,Intermediate (13) 1.63 g (5.63 mmol0.29 g (0.25 mmol) of Pd(PPh3)4,100 mL of toluene,50 mL of EtOH and 5.12 mL (10.2 mmol) of 2M K2CO3 were mixed, it was refluxed. After the reaction was completed, the reaction mixture was cooled at room temperature and the resulting solid was filtered with EtOH.The solid was dissolved in chloroform and purified by silica gel column chromatography (CHCl3: HEX). Ethyl acetate (EA) was solidified and filtered to obtain 1.62 g (yield: 55.7%) of a beige solid compound 4-415 (WS16-30-211).
With copper(II) acetate monohydrate; sulfur; sodium hydroxide; In dimethyl sulfoxide; at 130.0℃; for 24.0h;Sealed tube; Inert atmosphere;
General procedure: A mixture of o-iodoaniline (0.5 mmol, 1 equiv), arylacetic acid (0.6 mmol), elemental sulfur (1.5mmol), Cu(OAc)2·H2O (20 mmol%), and NaOH (1.0 mmol) in DMSO (3 mL) was put into a sealed pressure vessel (25 mL) containing a magnetic stirring bar. The tube was purged with nitrogen three times, and then capped and stirred in a preheated oil bath at 130 C for 24 h. The reaction mixture then cooled to room temperature and extracted with ethyl acetate (3x10 mL), the organic layer was washed with saturated NaCl (2x10 mL), dried over anhydrous Na2SO4, evaporated under vacumm and then purified by silica gel column chromatography by using petroleum ether and ethyl acetate (PE:EA=200:1) as eluent.
With potassium phosphate; tetrakis(triphenylphosphine) palladium(0); In ethanol; water; toluene; for 3.0h;Reflux;
Intermediate 6 (10.4 g, 35.8 mmol), intermediate 7 (9.20 g, 39.3 mmol), a mixed solution of toluene / ethanol (2: 1, 195 mL), aqueous tripotassium phosphate (2.0 M, ) Were sequentially added, and nitrogen bubbling was carried out for 30 minutes.Pd (PPh 3) 4 (1.00 g, 0.87 mmol) was added thereto, and the mixture was stirred for 3 hours while heating under reflux. After returning to room temperature, distilled water was added and extraction was carried out using toluene.The organic layer was washed with a saturated aqueous sodium chloride solution, dried over magnesium sulfate, and the solvent was distilled off under reduced pressure. The residue was subjected to silica gel column chromatography to give Intermediate 8 (13.6 g, yield 95%). Intermediate 6 was synthesized by referring to the method described in International Publication No. 2015/087961.
With potassium phosphate; tetrakis(triphenylphosphine) palladium(0); In ethanol; water; toluene; for 3.0h;Reflux;
Intermediate 6 (29.8 g, 103 mmol), m-terphenylboronic acid(30.0 g, 109 mmol), a mixed solution of toluene / ethanol (2: 1, 300 mL) and an aqueous solution of tripotassium phosphate (2.0 M, 135 mL) were added in that order, followed by nitrogen bubbling for 30 minutes.Pd (PPh 3) 4 (3.10 g, 2.68 mmol) was added thereto, and the mixture was stirred for 3 hours while heating under reflux. After returning to room temperature, distilled water was added and extraction was carried out using toluene.The organic layer was washed with a saturated aqueous sodium chloride solution, dried over magnesium sulfate, and the solvent was distilled off under reduced pressure. The residue was subjected to silica gel column chromatography to give Intermediate 14 (36.9 g, yield 82%).
45.9 g
With potassium phosphate; tetrakis(triphenylphosphine) palladium(0); In ethanol; water; toluene; at 100.0℃; for 4.0h;Inert atmosphere;
In a 1-L eggplant flask, 31.7 g of 2- (3-bromophenyl) benzothiazole,B- [1,1 ?: 3 ?, 1 ? -terphenyl] -3-ylboronic acid: 33.7 g,Tetrakis (triphenylphosphine) palladium (0): 2.2 g is put,Furthermore, nitrogen bubbled toluene: 350 mL, ethanol: 100 mL, and 2M tripotassium phosphate aqueous solution: 200 mL were added, and the mixture was stirred at 100 C. for 4 hours.After cooling to room temperature, the aqueous phase was removed, the solvent was removed, and the resulting residue was subjected to silica gel column chromatography (gel 600 mL,Dichloromethane / hexane = 3/7 ? 5/5) to obtain 45.9 g of intermediate 4.
With silver(I) 4-methylbenzenesulfonate; In water; at 100.0℃; for 12.0h;Sealed tube; Inert atmosphere; Green chemistry;
General procedure: A sealed pressure vessel was charged with benzothiazole (68 mg, 0.5 mmol), AgOTs (280 mg, 1 mmol),aldehyde (0.6 mmol) and 2.0 mL of H2O. The resulting solution was stirred at 100 C for 12 h under N2.Upon completion of the reaction, H2O (8.0 mL) was added, then extracted with EtOAc (5 mL × 3), driedover Na2SO4, and concentrated under reduced pressure. The residue was further purified with flashcolumn chromatography.
34%
With tert.-butylhydroperoxide; N-chloro-succinimide; In decane; dimethyl sulfoxide; at 120.0℃; for 10.0h;Schlenk technique;
Weigh 2-bromo-benzaldehyde (0.37 mmol, 68.8 mg) benzothiazole (1.0 eq., 0.37 mmol, 50.0 mg), NCS (30 mol%, 0.11 mmol, 14.7 mg) and 5.5 M TBHP in decane (1.5 eq., 0.37 mmol, 67 muL) in a 25 mL Schlenk reaction tube, and then added DMSO (20 eq., 7.4 mmol, 0.58 g), placed at 120 reaction, 12 hours later the reaction was completed, the reaction solution was extracted with DCM, The organic layer was concentrated to remove the solvent, and the concentrated liquid was separated by column chromatography (eluent is a petroleum ether-ethyl acetate mixed solvent with a volume ratio of 1: 0.1) to obtain a white solid, namely the derivative Im. The yield is 80%.
With methanesulfonic acid; di-tert-butyl peroxide; copper(II) oxide; at 120.0℃; for 20.0h;
0.06 mmol of cuprous oxide, 0.3 mmol of o-aminothiophenol, 1.2 mmol of di-tert-butyl peroxide,And 0.3 mmol of methanesulfonic acid was added to 2 mL of 3-bromotoluene,It was refluxed at 120 C for 20 hours. After the reaction is completed,Cool to room temperature,The reaction mixture was diluted with 30 mL of ethyl acetate.Then use 8 mL of saturated brine,8mL of NaHSO3 solution,Wash with 8 mL of saturated saline solution.Dry with anhydrous Na2SO4, suction filtration, spin dry,Finally, using thin layer chromatography or column chromatography(Petroleic ether / ethyl acetate) isolated product 51.3 mg,The yield was 59%.
General procedure: After observing the high activity of the (CuII-NHCs)nnSiO2 in the synthesis of benzimidazoles, we were encouraged to apply this catalyst in the synthesis of benzothiazoles. In this manner, the reaction between 3-bromobenzaldehyde and 2-ATP was used as model reaction for optimization of reaction conditions. In this situation, the effect of important parameters such as solvent type, catalyst amount and reaction temperature were investigated (Table 2). The obtained results showed that the highest benzothiazole was produced by 0.020mol% of (CuII-NHCs)nnSiO2 catalyst at room temperature and under solvent free conditions Table 2, entries 12-19). To investigate the scope and generality of the catalyst, different substituted benzaldehydes were reacted with 2-aminothiophenol and the corresponding 2-sunstituted benzothiazoles were produced in 85-95% (Table 4 , entries 1-8). The benefits of this catalytic system include high catalyst activity, short reaction time and easy separation of the catalyst from the product.
With trifluorormethanesulfonic acid; In neat (no solvent); at 100.0℃; for 12.0h;
General procedure: A reaction flask was charged with a mixture of 1a (3.0 mmol), 2a (3.0 mmol), TfOH (0.06 mmol). The reaction mixture was stirred at 100 oC for 12 h, and then was cooled to room temperature. Water (10 mL) was added to the resultant mixture. The product was extracted with CH2Cl2 (10 mL × 2). The solvent was removed under reduced pressure, and the residue obtained was purified via silica gel chromatography (eluent: petroleum ether/ethyl acetate = 50:1) to afford the product 3a (595.8mg, 94% yield) as a white solid.
Chemistry
Pharmaceutical Intermediates
Inhibitors/Agonists
Material Science
For Research Only
110K+ Compounds
Competitive Price
1-2 Day Shipping
