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Structure of 2491-36-3 * Storage: {[proInfo.prStorage]}
* 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 perchloric acid; C13H9BrN3O4V; dihydrogen peroxide; potassium bromide In water at 20℃; for 0.583333 h;
General procedure: In a 50mL round bottom flask equipped with a magnetic stirringbar, 2-hydroxyacetophenone (10 mmol) were added. To this solution,KBr (40 mmol) dissolved in 20 mL water was added and thendissolved by stirring at ambient temperature followed by additionof a 30percent H2O2 (4 mmol). To this reaction mixture, vanadium(V)complex (0.01 mmol) and 70percent HClO4 (4 mmol) were added and thereaction mixture was stirred at 0 C and then after 10 min at roomtemperature. An additional 4 mmol of 70percent HClO4was further addedin three equal portions after every 10 min with continuous stirring.In addition, all the reactions were monitored using thin layerchromatography. The NMR spectra of bromination products aregiven in the supporting information.
72%
With N-Bromosuccinimide; toluene-4-sulfonic acid In acetonitrile at 80℃;
General procedure: A modified reaction route: NBS (1.2 equiv.) was added to a solution of appropriately substitutedacetophenones 9a–9l (1.0 equiv.) in CH3CN (15 mL) with p-TSA (0.2 equiv.). The solution washeated at 80 °C for 3-5 h until all the starting materials had been consumed (TLC monitored). Thereaction mass was poured in ice-cold water and extracted with DCM (3 × 20 mL). Anhydrous Na2SO4was added to the combined organic layer, filtered and the excess solvent was removed under reducedpressure. The resultant solid/ liquid obtained were washed with hexane to yield compounds 10a–10i.4,5
Reference：
[1] Tetrahedron Letters, 2009, vol. 50, # 6, p. 700 - 703
[2] Tetrahedron, 2001, vol. 57, # 11, p. 2203 - 2211
[3] Archiv der Pharmazie, 2009, vol. 342, # 9, p. 541 - 545
[4] Synthetic Communications, 2006, vol. 36, # 19, p. 2877 - 2881
[5] Journal of Organometallic Chemistry, 2018, vol. 876, p. 10 - 16
[6] Indian Journal of Chemistry - Section B Organic and Medicinal Chemistry, 2003, vol. 42, # 2, p. 408 - 411
[7] Organic Letters, 2015, vol. 17, # 19, p. 4890 - 4893
[8] Bioorganic and Medicinal Chemistry Letters, 2018, vol. 28, # 17, p. 2861 - 2864
[9] Indian Journal of Chemistry - Section B Organic and Medicinal Chemistry, 2005, vol. 44, # 1, p. 184 - 187
[10] RSC Advances, 2014, vol. 4, # 107, p. 62308 - 62320
[11] Revue Roumaine de Chimie, 2010, vol. 55, # 11-12, p. 983 - 987
[12] ACS Medicinal Chemistry Letters, 2016, vol. 7, # 7, p. 686 - 691
[13] Journal of Medicinal Chemistry, 1971, vol. 14, # 10, p. 977 - 982
[14] Synthetic Communications, 1990, vol. 20, # 6, p. 809 - 816
[15] Journal of Chemical Research - Part S, 2001, # 11, p. 472 - 473
[16] Tetrahedron Letters, 2007, vol. 48, # 8, p. 1411 - 1415
[17] Patent: US6329399, 2001, B1,
[18] Bioorganic and Medicinal Chemistry Letters, 2008, vol. 18, # 1, p. 141 - 146
[19] Bioorganic and Medicinal Chemistry Letters, 2010, vol. 20, # 7, p. 2259 - 2263
[20] Synthesis, 2010, # 5, p. 811 - 817
[21] Chemical Biology and Drug Design, 2011, vol. 78, # 6, p. 979 - 987
[22] Journal of Fluorescence, 2011, vol. 21, # 6, p. 2173 - 2184
[23] Journal of Photochemistry and Photobiology B: Biology, 2012, vol. 115, p. 25 - 34
[24] Journal of Fluorescence, 2015, vol. 25, # 6, p. 1727 - 1738
[25] Letters in Organic Chemistry, 2016, vol. 13, # 9, p. 672 - 677
[26] Patent: CN105315252, 2016, A, . Location in patent: Paragraph 0056-0058
[27] Journal of the Chinese Chemical Society, 2017, vol. 64, # 12, p. 1408 - 1416
[28] Bioorganic and Medicinal Chemistry Letters, 2018, vol. 28, # 4, p. 668 - 672
[29] Archiv der Pharmazie, 2018, vol. 351, # 3-4,
[30] Bioorganic and Medicinal Chemistry, 2018, vol. 26, # 8, p. 1986 - 1995
2
[ 40231-08-1 ]
[ 2491-36-3 ]
Yield
Reaction Conditions
Operation in experiment
70%
With hydrogenchloride In water for 4 h; Reflux
General procedure: The viscous liquid which is obtained from step s1.2 was hydrolysed by the suitable hydrochloric acid in aqueous media for 4 h under reflux condenser. The reaction mixture was poured into ice-water. The crystalline raw product was filtered,washed with water and three times recrystallized from ethanol.
Reference：
[1] Letters in Organic Chemistry, 2016, vol. 13, # 9, p. 672 - 677
3
[ 582-24-1 ]
[ 2491-36-3 ]
Yield
Reaction Conditions
Operation in experiment
60%
for 2 h; Reflux
General procedure: A solution of bromine (0.27 mL, 5 mmol) inacetic acid (10 mL) is added stepwise to a solution of DHA 1 (0.84 g, 5 mmol) in acetic acid (20 mL). After a reflux of 2h, the reaction mixture was poured into water (100 mL) and ice (50 g). The obtained solid was filtered-off andrecrystallized from a 1:1 mixture of hexane-chloroform, being compound 2c obtained as yellow crystals (0.75 g, 61percent):mp 117°C (mp 118-119 ).
With polymeric resin-bound hexafluorophosphate ion; In methanol; water; at 20℃; for 7.0h;
General procedure: In a typical experimental procedure, o-phenlylenediamine and alpha-bromo ketone in 1:1 molar ratios was taken in a 100 mL round bottom flask. To this water-methanol (1:1) and 100 mg PHP was admixed. The reaction mixture was then allowed to stir with magnetic spinning bar, after some time a yellowish mass appeared which settles down like a precipitate after the completion of the reaction (checked by TLC). It was then filtered; the solid reaction mixture was dissolved with dichloromethane (25 mL) and evaporated under vacuum. The crude product was then crystallised from ethanol. The desired product was pure on TLC and characterized by spectral (IR, 1H and 13C NMR) data and compared to those reported in literature.
General procedure: General procedure for the synthesis of alpha-azidoacetophenones (3a-g) Without further purification, alpha-bromoacetophenone 2a (1.8 g, 6.02 mmol) was dissolved in acetone (15 mL) and solid NaN3 (0.5 g, 7.69 mmol) dissolved in water (3 mL) added to the reaction mixture. The reaction mixture was stirred for 30 min. After the completion of the reaction, acetone was evaporated, diluted with EtOAc and washed with water. The organic layer was separated and dried with Na2SO4.The solvent was evaporated and purified by column chromatography using pet ether-ethyl acetate (98:2) yielded alpha-azidoacetophenone (3a). The above mentioned procedure was carried out for the synthesis of substituted alpha-azidoacetophenones (3b-g) from their corresponding alpha-bromoacetophenones.
With potassium carbonate; In water; N,N-dimethyl-formamide; at 20℃;
General procedure: A mixture of the alpha-bromoketone (8a-h, 1mmol, 1eq), imidazole (3mmol, 3eq), and anhydrous K2CO3 (3mmol, 3eq) in DMF (3mL) was stirred at room temperature for 2-3h. The reaction mixture was diluted with H2O (10mL) and extracted with EtOAc (15mL, twice). The combined organic phase was washed sequentially with H2O (10mL) and brine (10mL). The combined organic extracts were dried over Na2SO4, and evaporated. High-vacuum drying gave crude 9a-h. A solution of crude 9a-h (1mmol, 1eq) in methanol (4mL) was added to a suspension of sodium borohydride (1mmol, 1eq) in anhydrous methanol (20mL) maintaining the temperature below 5C under atmospheric pressure. The resulting mixture was stirred at room temperature for 1h and then heated to 50C for 1h. After cooling to room temperature the reaction mixture was concentrated and water (8mL) was added. The product was extracted with ethyl acetate (10mL, twice). The organic phase was dried over Na2SO4 and purified by flash chromatography on silica gel using MeOH-EtOAc (6:94) as the eluent to afford the imidazole alcohol (10a-10h); overall yields up to 77%.
With perchloric acid; dihydrogen peroxide; potassium bromide; In water; at 0 - 20℃; for 0.583333h;
General procedure: In a 50mL round bottom flask equipped with a magnetic stirringbar, 2-hydroxyacetophenone (10 mmol) were added. To this solution,KBr (40 mmol) dissolved in 20 mL water was added and thendissolved by stirring at ambient temperature followed by additionof a 30% H2O2 (4 mmol). To this reaction mixture, vanadium(V)complex (0.01 mmol) and 70% HClO4 (4 mmol) were added and thereaction mixture was stirred at 0 C and then after 10 min at roomtemperature. An additional 4 mmol of 70% HClO4was further addedin three equal portions after every 10 min with continuous stirring.In addition, all the reactions were monitored using thin layerchromatography. The NMR spectra of bromination products aregiven in the supporting information.
84%
With perchloric acid; [(CH3)2NH2]2[(VO2)2(slox)].2H2O; dihydrogen peroxide; potassium bromide; In water; at 0℃; for 0.5h;
General procedure: Salicylaldehyde (0.24 g, 2 mmol) was taken in a 50 mL roundbottom flask maintained at 0 C, KBr (0.47 g, 4 mmol) dissolvedin 5 mL water was added, followed by the addition of 30% H2O2(1.70 g, 15 mmol). To this reaction mixture, the vanadium(V) complexes1-3 (0.05 mmol) and 70% HClO4 (0.14 g, 1 mmol) wereadded and the reaction mixture was stirred at 0 C. An additional1 mmol of 70% HClO4 was further added in three equal portionsafter every 10 minutes, with continuous stirring. A light brownsolid product was obtained which was separated using a separating funnel. The crude product thus obtained was then purifiedby column chromatography to afford the desired product. TheNMR spectra of the bromination products are given in the Supportinginformation.
72%
With N-Bromosuccinimide; toluene-4-sulfonic acid; In acetonitrile; at 80℃;
General procedure: A modified reaction route: NBS (1.2 equiv.) was added to a solution of appropriately substitutedacetophenones 9a-9l (1.0 equiv.) in CH3CN (15 mL) with p-TSA (0.2 equiv.). The solution washeated at 80 C for 3-5 h until all the starting materials had been consumed (TLC monitored). Thereaction mass was poured in ice-cold water and extracted with DCM (3 × 20 mL). Anhydrous Na2SO4was added to the combined organic layer, filtered and the excess solvent was removed under reducedpressure. The resultant solid/ liquid obtained were washed with hexane to yield compounds 10a-10i.4,5
In chloroform; ethyl acetate;
Preparation Example 16 Preparation of 2-bromo-2'-hydroxyacetophenone Ethyl acetate (40 ml), was mixed with 13.8 g (61.8 mmol), of copper dibromide, and a solution of 5.00 g (37.0 mmol), of o-hydroxyacetophenone in 40 ml of chloroform was dropped while refluxing with heating, the mixture being refluxed for additional 4 hours. White crystals precipitated were filtered and the filtrate was washed with water and with saturated saline and dried with anhydrous sodium sulfate. Then the solvent was distilled off under reduced pressure. The raw material, o-hydroxyacetophenone, was removed from the resulting residue by distillation under reduced pressure to obtain 4.12 g (yield: 51.8%), of the target compound as a pale yellow oily substance. 1H-NMR (CDCl3, ppm) 4.45 (s, 2 H), 6.91~7.01 (m, 2 H), 7.53 (m3 1 H), 7.74 (m, 1 H), 11.7 (s, 1 H)
With N-Bromosuccinimide; In diethyl ether; at 20℃;Irradiation; Inert atmosphere;
General procedure: General procedure for the synthesis of alpha-bromoacetophenones (2a-g): Acetophenone 1a (1.0 g, 8.3 mmol) was dissolved in 20 mL diethyl ether in a two neck round bottom flask and recrystallised NBS (2.9 g, 16.8 mmol) was added portion wise. The reaction was irradiated using Philips HPL-N (250 W, lambda = 200-600 nm) lamp fitted with a water circulation arrangement at room temperature under nitrogen atmosphere. After completion of the reaction, the reaction mixture was filtered, diluted with ether and washed with water. The organic layer was separated, dried with Na2SO4 and the solvent was removed under vacuum to yield alpha-bromoacetophenone (2a). Similar procedure was followed for the synthesis of substituted alpha-bromoacetophenones (2b-g).
With copper(I) bromide; In chloroform; ethyl acetate; at 20 - 90℃;
16. 4 g of copper bromide (0.074 mol) was homogeneously ground, dissolved in 20mL chloroform. 5 g o-hydroxyacetophenone (0. 037 mol) was placed in a 250 mL eggplant flask, dissolved in 20 mL of ethyl acetate. The reaction solution was added dropwise using a constant pressure dropping funnel, and stirred at room temperature. After dripping was finished, the reaction flask was placed in an oil bath, oil bath temperature set at 90 C, and heated to reflux. After completion of the reaction, the reaction solution was completely changed from dark green to amber. The reaction solution was filtered while it was still hot with diatomaceous earth, and the filter cake was washed with ethyl acetate. The resulting filtrate was evaporated under reduced pressure to remove the solvent. The crude product was an oil, which is directly used for next step.
With copper(ll) bromide; In ethyl acetate; for 12.0h;Reflux;
General procedure: In the synthesis process, different 1-(aryl/heteroaryl)ethanone(50 mmol) derivatives were brominated in the presence of copper(II) bromide (100 mmol) followed by a reaction with equimolarpyrimidine-2-carbothioamide (50 mmol). In the course of the reaction,the components were mixed in ethanol acetate for approximately1 h in room temperature and then refluxed at 77-78 Cfor 15-20 min. After cooling, the precipitate was filtered, neutralizedwith sodium acetate, and recovered from the HBr salt. Allthe synthesized compounds were purified twice by crystallizationfrom ethanol. Pyrimidine-2-carbonitrile and phosphorus pentasulfidewere mixed in dioxane for 48 h to obtain pyrimidine-2-carbothioamideas the starting material. This is the first time in theliterature that synthesis of pyrimidine thioamides has been undertakenwith this method
With bromine; acetic acid; at 10℃; for 2.0h;
A mixture of alpha-acetophenone, 1, and bromine in acetic acid was stirred below 10C for 2 hrs, to yield o-hydroxyphenacyl bromide [18, 19]. 1H NMR (CDCl 3 , 300MHZ, delta): 4.478 (s, 3H, CH 2 ), 7.989-8.018 (d, 2H, Ar-H), 7.488-7.657 (t, 3H, Ar-H).
EXAMPLE 6 A solution of 2-bromo-2'-hydroxyacetophenone (11.25 g) in acetonitrile (25 ml) was added dropwise, with stirring and cooling, to a solution of 1,2,4-triazole (3.45 g) and triethylamine (5.05 g) in acetonitrile (75 ml). The temperature was maintained at -20 C. for 3 hours with continued stirring. The reaction mixture was allowed to warm to room temperature and stirred overnight. The mixture was filtered and the solvent evaporated. The residue was triturated with ethyl acetate and some solid filtered off. The filtrate was chromatographed using ethyl acetate as eluent to give crude 2'-hydroxy-2-(1,2,4-triazol-1-yl)acetophenone.
With triethylamine; In acetonitrile;
Example 6 A solution of 2-bromo-2'-hydroxyacetophenone (11.25g) in acetonitrile (25ml) was added dropwise, with stirring and cooling, to a solution of 1,2,4-triazole (3.45g) and triethylamine (5.05g) in acetonitrile (75ml). The temperature was maintained at -20C for 3 hours with continued stirring. The reaction mixture was allowed to warm to room temperature and stirred overnight. The mixture was filtered and the solvent evaporated. The residue was triturated with ethyl acetate and some solid filtered off. The filtrate was chromatographed using ethyl acetate as eluent to give crude 2'-hydroxy-2-(1,2,4-triazol-1-yl)acetophenone.
Example 1 Synthesis of 2'-hydroxy-2-(4-hydroxyphenylthio)acetophenone (Compound No. I-4) 10.0 g (79.4 mmol) of 4-mercaptophenol, 5.3 g (80.4 mmol) of potassium hydroxide and 100 mL of methanol were added under a room temperature into a 200 mL flask with four inlets and attached with a stirrer and a thermometer. After confirming that potassium hydroxide added is completely dissolved, temperature inside the resultant solution was cooled down to 10C, then 16. 9 g (78.6 mmol) of 2'-hydroxyphenacyl bromide was added to the solution and stirred for 3 hours at a room temperature. Following to the completion of the reaction, the solution was extracted with methyl isobutyl ketone, hereinafter referred to as MIBK, and MIBK was distilled out of the extract under reduced pressure. The obtained residue was subjected to recrystallization process with toluene to thereby obtain 19.0 g of 2'-hydroxy-2-(4-hydroxyphenylthio)acetophenone. The yield was 93% and the melting point thereof was in a range of 139 to 141C.
General procedure: A mixture of equimolar quantities of 5-cyclopropyl-1,3,4-thiadiazol-2-amine (0.01 mol) 3 and substituted phenacyl bromides (0.01 mol) was refluxed in dry ethanol for 16 h. The excess of solvent was distilled off and the solid hydrobromide that separated was collected by filtration, suspended in water and neutralized by aqueous sodium carbonate solution to get free base 4(a-k). It was filtered, washed with water, dried and recrystallized from ethanol.
Step 1. Synthesis of 2-[2-(trifluoromethyl)-1,3-thiazol-4-yl]phenol (C4) 2,2,2-Trifluoroethanethioamide (which may be prepared by the method of J. H. Hillhouse et al., Phosphorus, Sulfur Relat. Elem. 1986, 26, 169-84) (157 mg, 1.22 mmol) in ethanol (1.3 mL) was added drop-wise to a solution of 2-bromo-1-(2-hydroxyphenyl)ethanone (119 mg, 0.55 mmol) in ethanol (1.3 mL) and the reaction was refluxed overnight. The reaction was concentrated in vacuo and purified via silica gel chromatography (Gradient: 5% to 20% ethyl acetate in heptane) to afford the title compound. Yield: 67 mg, 0.27 mmol, 49%. LCMS m/z 246.0 (M+1). 1H NMR (400 MHz, CDCl3) delta 6.95 (ddd, J=8, 7, 1 Hz, 1H), 7.07 (dd, J=8.2, 1.2 Hz, 1H), 7.33 (ddd, J=8, 7, 2 Hz, 1H), 7.64 (dd, J=7.8, 1.6 Hz, 1H), 7.81 (s, 1H), 10.47 (s, 1H).
General procedure: A mixture of allyl bromide (2.0 mmol), indium powder (1.0mmol), and alpha-bromoketone (1.0 mmol) in THF/H2O (0.5mL:1.5mL) was stirred at ambient temperature. Reaction was monitored by TLC until no starting material was observed and normally the reaction mixture was stirred at rt overnight. The reaction mixture was then extracted with Et2O (5mL×2). The combined organic layers were washed with brine (3mL×2), dried over MgSO4, and concentrated in a rotary evaporator. The residue was purified by silica-gel chromatography using Et2O/hexanes (1:20) as eluent to give the product (219 mg, 85%). An oil; TLC (Et2O/hexanes (1:4)) Rf=0.12; 1H NMR (300 MHz, CDCl3) delta 2.83 (dd, J=7.8, 0.9 Hz, 2H), 3.28 (s, 1H), 3.72 (d, J=10.8 Hz, 1H), 3.91 (d, J=10.8 Hz, 1H), 5.14-5.21 (m, 2H), 5.60-5.74 (m, 1H), 6.80-6.88 (m, 2H), 6.99 (dd, J=7.8, 1.5 Hz, 1H), 7.15-7.21 (m, 1H), 8.73 (s, 1H); 13C NMR (75 MHz, CDCl3) delta 42.6 (CH2), 43.1 (CH2), 77.8 (C), 118.1 (CH), 119.6 (CH), 120.4 (CH2), 124.0 (C), 126.7 (CH), 129.7 (CH), 131.8 (CH), 156.2 (C); IR (neat) 3242, 2978, 1583 cm-1; APCI-MS m/z (rel intensity) 241 (41), 239 ([M+H-H2O]+, 45), 177 (10), 159 (100); HRMS [M+H-H2O]+ for C11H12BrO: 239.0066, found 239.0072.
2-(2-(2-(1H-indol-3-yl)ethylimino)-3-phenyl-2,3-dihydrothiazol-4-yl)phenol[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
81%
With triethylamine; In acetonitrile; for 0.75h;Reflux;
General procedure: The solution of 1-(2-(1H-indol-3-yl)ethyl)-3-phenylthiourea 3a (1 mmol), 2-bromoacetophenone 4 (1mmol) and triethylamine (1 mmol) in acetonitrile (2 mL) was refluxed for 45 min. The progress of the reaction was followed by TLC examination using hexane ethyl acetate (3:7, v/v). On completion of the reaction the products were extracted using ethyl acetate and dried over anhydrous sodium sulphate and concentrated under vacuum to obtain compound 5, which was recrystallized from ethanol or methanol to obtained (5a-o) crystalline solids.
1-(2-(1H-indol-3-yl)ethyl)-3-(4-chlorophenyl)thiourea[ No CAS ]
[ 2491-36-3 ]
2-(2-(2-(1H-indol-3-yl)ethylimino)-3-(4-chlorophenyl)-2,3-dihydrothiazol-4-yl)phenol[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
76%
With triethylamine; In acetonitrile; for 0.75h;Reflux;
General procedure: The solution of 1-(2-(1H-indol-3-yl)ethyl)-3-phenylthiourea 3a (1 mmol), 2-bromoacetophenone 4 (1mmol) and triethylamine (1 mmol) in acetonitrile (2 mL) was refluxed for 45 min. The progress of the reaction was followed by TLC examination using hexane ethyl acetate (3:7, v/v). On completion of the reaction the products were extracted using ethyl acetate and dried over anhydrous sodium sulphate and concentrated under vacuum to obtain compound 5, which was recrystallized from ethanol or methanol to obtained (5a-o) crystalline solids.
1-(2-(1H-indol-3-yl)ethyl)-3-(4-fluorophenyl)thiourea[ No CAS ]
[ 2491-36-3 ]
2-(2-(2-(1H-indol-3-yl)ethylimino)-3-(4-fluorophenyl)-2,3-dihydrothiazol-4-yl)phenol[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
73%
With triethylamine; In acetonitrile; for 0.75h;Reflux;
General procedure: The solution of 1-(2-(1H-indol-3-yl)ethyl)-3-phenylthiourea 3a (1 mmol), 2-bromoacetophenone 4 (1mmol) and triethylamine (1 mmol) in acetonitrile (2 mL) was refluxed for 45 min. The progress of the reaction was followed by TLC examination using hexane ethyl acetate (3:7, v/v). On completion of the reaction the products were extracted using ethyl acetate and dried over anhydrous sodium sulphate and concentrated under vacuum to obtain compound 5, which was recrystallized from ethanol or methanol to obtained (5a-o) crystalline solids.
2-(7-methylaminoimidazo[1,2-a]pyridin-2-yl)phenol[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
14%
With toluene-4-sulfonic acid; In acetone; for 16.0h;Inert atmosphere; Reflux;
To a solution at 25 C under nitrogen of N4-methyl-pyridine-2,4-diamine (200 mg, 1.62 mmol) in acetone (10 ml) was added 2-bromo-l-(2-hydroxyphenyl)ethanone (603 mg, 2.47 mmol) and pTSA (catalytic amount). The mixture was stirred for 30 min at 25 C and then allowed to reflux for another 16 h. Volatilities were removed under vacuum. The resultant crude material was purified by column chromatography using amine bound silica gel (70 % EtOAc/hexane) to afford 2-(7-methylamino-imidazo[l,2-a]pyridin-2-yl)-phenol as yellow solid (55 mg, 14 ). MS m/z: 239.6 [M+H]+.
2-(2-m-tolylimidazo[2,1-b][1,3,4]thiadiazol-6-yl)phenol[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
64%
In ethanol; for 24h;Reflux;
General procedure: A mixture of equimolar quantities of <strong>[76074-47-0]5-m-tolyl-1,3,4-thiadiazol-2-amine</strong> 8 (0.01mol) and substituted phenacyl bromides (0.01mol) was refluxed in dry ethanol (50mL) for 24h. The excess of solvent was distilled off and the solid hydrobromide salt that separated out was collected by filtration, suspended in water and neutralized by sodium carbonate to get free base 9(a-i). The product was filtered, washed with water, dried and crystallized from carbon tetrachloride.
2-(2-(2,4-dichlorophenyl)imidazo[2,1-b][1,3,4]thiadiazol-6-yl)phenol[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
64%
In ethanol; for 24.0h;Reflux;
General procedure: A mixture of equimolar quantities of 5-(2,4-dichlorophenyl)-1,3,4-thiadiazol-2-amine 11 (0.01mol) and substituted phenacyl bromides (0.01mol) was refluxed in dry ethanol (50mL) for 24h. The excess of solvent was distilled off and the solid hydrobromide salt that separated out was collected by filtration, suspended in water and neutralized by sodium carbonate to get free base 12(a-g). The product was filtered, washed with water, dried and crystallized from carbon tetrachloride.
General procedure: A mixture of 10 mmol of acrylic acid thioamide VII and 10 mmol of alpha-bromoketone II in 25 mL of DMF was stirred at 20C for 30 min and then left standing for 24 h. The reaction mixture was diluted with an equal volume of water, and the resulting precipitate was filtered off.
With triethylamine; In isopropyl alcohol; for 8.0h;Reflux;
General procedure: A mixture of 10 mmol of thiopyran I, 10 mmol of alpha-bromoketone II, and 1.4 mL (10 mmol) of triethylamine in 25 mL of 2-propanol was refluxed for 8 h and filtered. After 48 h the precipitate was separated, washed with 2-propanoland hexane, and recrystallized from butanol.
General procedure: alpha-Bromoarylethanones (deliquescent) were prepared accordingto the reported method [18]. The ethanolic mixture of alpha-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 1
63%
With iodine; In N,N-dimethyl-formamide; at 100℃;
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. 5
2-(2-[2-(trifluoromethyl)phenyl]amino-1,3-thiazol-4-yl)phenol[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
67%
In ethanol; at 70℃; for 2.0h;
General procedure: Compounds 17-29and 43-61 were prepared following this general protocol unless otherwise noted. To substituted2-bromoethanone in ethanol was added substituted thiourea (1.02 eq). The mixture wasstirred at 70C. The reaction was monitored via LC/MS. After 2 h, the reaction mixture wascooled to room temperature and precipitate was formed. The precipitate was collected by vacuumfiltration and washed with acetone. The solid was dissolved in 2 MNaOH (25 mL) and extracted with EtOAc (3 x 50 mL). The combined organic layers were dried over Na2SO4 andconcentrated in vacuo desired product.
2-[2-(3-(4'-methoxyphenyl)-5-phenyl-2-pyrazolin-1-yl)thiazol-4-yl]phenol[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
80%
In ethanol; for 4.0h;Reflux;
General procedure: A mixture of 3-(4'-methoxyphenyl)-5-phenyl-2-pyrazolin-1-carbothioamide (5) (0.001 mol) and 2-bromoacetophe-none (0.001 mol) in ethanol (20 mL) was refluxed for 4 h. The reaction mixture was cooled and filtered.
2-(2′-hydroxyphenyl)imidazo[1,2-a]pyridine[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
79%
With sodium hydrogencarbonate; In ethanol; for 2.0h;Reflux;
General procedure: To a solution of 2-aminopyridine (1.0 equiv.) in EtOH (15 mL) was added the appropriate 10a-10f or10h (1.0 mmol) with NaHCO3 (0.5 equiv.). The solution was refluxed about 2 h. After completion ofthe reaction (monitored by TLC), the formed precipitate was filtered off and washed with acetone (15mL). The aqueous phase was extracted with DCM (3 × 20 mL). The combined organic layers weredried on Na2SO4, filtered and concentrated) under vacuum to give the pure imidazo[1,2-a]pyridine13a-13g. 6, 7
With 1,4-diaza-bicyclo[2.2.2]octane; In water; at 60℃; for 4.0h;
Compound 1 or compound 2 in a molar ratio of 1:1, DABCO to the mol percentage of 10% (with compound 1 as heretofore), wherein the compound 1 amount is 5mmol, the solvent is 15 ml water, in sequentially adding a round-bottom flask, in 60 C stirring reaction under 4 hours. After the reaction is finished cooling, mixed solution diluted AcOEt, then using the saturated salt water (3×10 ml) wash, extraction, the organic phase is dried with anhydrous magnesium sulfate, and by short silica gel column, to remove the solvent by the spin vaporization of the filtrate, the residue by silica gel column chromatography for, petroleum ether/ethyl acetate mixed solvent washing, TLC detection, combined effluent contains product, rotating evaporimeter distilled to remove the solvent, vacuum drying to obtain the target product compound 3.
General procedure: The alpha-brominated structures which synthesized in previous step (s1), were dissolved in ethanol and thioacetamide orthiobenzamid was added to solution. The mixture was boiled for 4 hours under reflux condenser. When the reaction conclude,the reaction vessel became cold to room temperature,The sodium acetate solution (5M) was added to reaction mixture until neutralize. The crystalline raw product was filtered, washed with water and recrystallized from ethanol 3 times [6].
General procedure: The viscous liquid which is obtained from step s1.2 was hydrolysed by the suitable hydrochloric acid in aqueous media for 4 h under reflux condenser. The reaction mixture was poured into ice-water. The crystalline raw product was filtered,washed with water and three times recrystallized from ethanol.
The above N1-1 was placed in a 250 mL three-necked flask, 20 mL of acetic anhydride and 5 g of sodium acetate was added. The reaction flask was placed in an oil bath. The temperature of the reaction solution was raised to 120 C, and the reaction was stopped. The reaction solution was poured into 100 mL of ice water, extracted three times with ethyl acetate (25 mL * 3). The organic layers were combined, and the solvent was distilled off under reduced pressure. The crude product was placed in a 100 mL three-necked flask, The reaction flask was placed in an ice bath. To the reaction flask was slowly added 10 mL of concentrated sulfuric acid, The temperature of the reaction solution was controlled to less than 10 C. Concentrated sulfuric acid was added to the reaction flask. The reaction flask was placed in an oil bath, the reaction solution was heated to 50 C and reacted for 1h to stop the reaction. The reaction solution was poured into 200 mL of ice water, a large number of brown solids were precipitated and filtered to gave a cake. The crude product was isolated by column chromatography (ethyl acetate: petroleum ether 1: 100). The yield of the product, 1.32 g, was found to be (20.3%).
2-(5-methylimidazo[1,2-a]pyridin-2-yl)phenol[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
69%
In ethanol; at 60 - 70℃; for 3.0h;
General procedure: To a solution of 6-methylpyridin-2-amine 1 (0.01 mol) in 100 ml of ethanol, different derivative of phenacyl bromides 2a-l (0.01 mol) was added at RT. The reaction was heated at 60-70C and stirred for 3 h. Obtained crystalline solid was filtered, washed with warm ethanol and crystallized from 50% HCl.
(E)-2-(3-oxo-2,3-dihydro-1H-inden-1-ylidene)hydrazine-1-carbothioamide[ No CAS ]
[ 2491-36-3 ]
(E)-3-(2-(4-(2-hydroxyphenyl)thiazol-2-yl)hydrazono)-2,3-dihydro-1H-inden-1-one[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
89.5%
In ethanol; for 4.0h;Reflux;
General procedure: To a solution of 2a-2c (1.0 mmol) in ethanol (5 mL) was added substituted alpha-bromo ketone (1.0 mmol). After stirring at reflux for about 4 h, the reaction was cooled to room temperature and the formed solid was filtered off, dried and recrystallized to afford 3a-3l.
4-(2-hydroxyphenyl)-2-(pyrimidine-2-yl)thiazole[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
75%
In ethanol; at 20 - 78℃;
General procedure: In the synthesis process, different 1-(aryl/heteroaryl)ethanone(50 mmol) derivatives were brominated in the presence of copper(II) bromide (100 mmol) followed by a reaction with equimolarpyrimidine-2-carbothioamide (50 mmol). In the course of the reaction,the components were mixed in ethanol acetate for approximately1 h in room temperature and then refluxed at 77-78 Cfor 15-20 min. After cooling, the precipitate was filtered, neutralizedwith sodium acetate, and recovered from the HBr salt. Allthe synthesized compounds were purified twice by crystallizationfrom ethanol. Pyrimidine-2-carbonitrile and phosphorus pentasulfidewere mixed in dioxane for 48 h to obtain pyrimidine-2-carbothioamideas the starting material. This is the first time in theliterature that synthesis of pyrimidine thioamides has been undertakenwith this method.
General procedure: A solution of bromine (0.27 mL, 5 mmol) inacetic acid (10 mL) is added stepwise to a solution of DHA 1 (0.84 g, 5 mmol) in acetic acid (20 mL). After a reflux of 2h, the reaction mixture was poured into water (100 mL) and ice (50 g). The obtained solid was filtered-off andrecrystallized from a 1:1 mixture of hexane-chloroform, being compound 2c obtained as yellow crystals (0.75 g, 61%):mp 117C (mp 118-119 ).
2-(4-amino-5-sulfonyl-4H-1,2,4-triazol-3-yl)phenol[ No CAS ]
[ 2491-36-3 ]
2,2'-(7H-[1,2,4]triazolo[3,4-b][1,3,4]thiadiazine-3,6-diyl)diphenol[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
50%
With acetic acid; In ethanol; for 2.0h;
General procedure: Equimolar amounts of the appropriate alpha-bromoacetyl derivative2a-e (1.0 mmol) and triazolylphenol 1 (0.2 g; 1.0 mmol)were dissolved in absolute EtOH (10 mL) containing a catalyticamount of AcOH (1 mL), and the mixture was heated for 2 h,then cooled to r.t. The resulting solid was collected by filtrationand washed with EtOH and Et2O to give the pure product.
2-(4-benzylpiperazin-1-yl)-1-(2-hydroxyphenyl)ethanone[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
987 mg
With potassium carbonate; potassium iodide; In chloroform; at 20℃;
In a round bottom flask, 1.3 g (6.05 mmol) of 2-bromo-2'-hydroxyacetophenone and 2.2 g (12.10 mmol) of 1-benzylpiperazine were added.After adding chloroform, it was dissolved, and then 4.1 g (30.25 mmol) of potassium carbonate and 0.1 g (0.6 mmol) of potassium iodide were added.After the reaction was carried out at room temperature, the mixture was filtered, washed three times with water and then evaporated.The product was further purified by using PE:EA1:1 column to obtain 987 mg.
987 mg
With potassium carbonate; potassium iodide; In chloroform; at 20℃;
1.3 g (6.05 mmol) of 2-bromo-2'-hydroxyacetophenone and 2.2 g (12.10 mmol) of 1-benzylpiperazine were added to a round bottom flask, and dissolved in chloroform. Further, 4.1 g (30.25 mmol) of potassium carbonate and 0.1 g (0.6 mmol) of potassium iodide were added. After the reaction was carried out at room temperature, the mixture was filtered, washed three times with water and then evaporated. The product was further purified by using PE:EA1:1 column to obtain 987 mg.
5-(quinoxalin-3-yl)-4H-1,2,4-triazole-3-thiol[ No CAS ]
[ 2491-36-3 ]
2-(3-(quinoxalin-2-yl)thiazolo[2,3-c][1,2,4]triazol-5-yl)phenol[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
82%
for 12.0h;Reflux;
General procedure: 5-(quinoxalin-3-yl)-4H-1,2,4-triazole-3-thiol (III) (1 mmol) was refluxed with appropriate arylacyl bromide (1 mmol) in 15 mL ethanol for 12 h. The reaction was monitored by TLC. After completion of the reaction, the product was left for cooling. The solid was filtered and the crude products were recrystallized from methanol (all synthesized compounds with their SMILE structures and activitiesare provided in Supplementary Materials).
3-[(E)-{1-[2-(4-(2-hydroxyphenyl)-1,3-thiazol-2-yl)hydrazinylidene]ethyl}]-2H-chromen-2-one[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
76%
With triethylamine; In ethanol; for 3.0h;Reflux;
General procedure: Coumarinyl thiosemicarbazone derivatives 1-3 (1 mmol),phenacyl bromide derivatives (1 mmol), triethyl amine (1 mmol) were taken in (15 mL) ethanol and refluxed for 3 h toafford hydrazinyl thiazole coumarins 4-23. Disappearance ofstarting material was assessed by thin layer chromatography.The precipitates were formed which were filtered and driedin vacuum. Pure products were obtained upon crystallizationfrom ethyl acetate and afforded good yields (Scheme 1).Synthesized derivatives 4-23 were characterized by spectroscopictechniques such as EI-MS, HREI-MS, 1H-NMR, and13C-NMR.
N-(4-(2-hydroxyphenyl)thiazol-2-yl)-2-hydroxy-4-methoxyacetophenone hydrazone[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
82.3%
In ethanol; at 80℃;
1 mmol of paeonol thiosemicarbazone, 1 mmol of compound 3b was added to a 100 mL round bottom flask, 20-80 mL of absolute ethanol was added, and the reaction was stirred at 80 C with stirring. The reaction progress was monitored by TLC (V petroleum ether: V ethyl acetate = 3:1). After the reaction is over, cool, passFiltration, washing with absolute ethanol, drying, recrystallization from anhydrous ethanol and chloroform to give a yellow solid 4b, yield 82.3%
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