* 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.
Reference：
[1] Organic and Biomolecular Chemistry, 2016, vol. 14, # 28, p. 6687 - 6690
2
[ 67237-53-0 ]
[ 1468-83-3 ]
Yield
Reaction Conditions
Operation in experiment
87%
for 8 h; Reflux
General procedure: The mixture of 3 (232 mg, 2.0 mmol) and S-COPNA (NP) resin (59 mg, 0.2 mmol) in H2O (4 mL) was stirred (600 rpm) for 8 h under reflux conditions (bath temp. 120 °C). The catalyst was filtered and washed with H2O and heptane. One drop of saturated NaHCO3 was added and the organic layer was evaporated under reduced pressure. The residue was purified by column chromatography with heptane–acetone (20:1) as eluent to afford 23 (225 mg, 84percent).
76%
at 80℃; for 12 h; Green chemistry
General procedure: Calculated amount of Ag salt (97.1 mg, 0.1 mmol) was weighed into a long necked glass vessel, followed by addition of alkyne (1 mmol). Internal standard n-dodecane (1mmol) and 3 mL water was then added. The whole set-up was placed in an oil bath at 80°C, stirred and heated for 12/24 hours. After completion of the reaction,3 mL EtOAc was added to it, stirred for 5 minutes and the organic layer was collected. The organic layer was passed through a very short column of silica to remove any impurities and subjected to GC-MS analysis.
Reference：
[1] Journal of the American Chemical Society, 2006, vol. 128, # 39, p. 12596 - 12597
[2] RSC Advances, 2015, vol. 5, # 102, p. 84328 - 84333
4
[ 40018-26-6 ]
[ 2802-08-6 ]
[ 1468-83-3 ]
Yield
Reaction Conditions
Operation in experiment
58%
With boron trifluoride diethyl etherate In tetrahydrofuran at 65℃; for 16 h;
1-(Thiophen-3-yl)ethanone: (E)-4-(Dimethylamino)but-3-en-2-one (1.5 g, 12.6 mmol, 2.00 equiv.) and boron trifluoride-diethyl etherate (1.8 g, 12.4 mmol, 2.00 equiv.) were added to a solution of 1,4-dithiane-2,5-diol (1 g, 6.51 mmol, 1.00 equiv.) in tetrahydrofuran (50 mL). The resulting solution was stirred at about 65° C. for about 16 hours, and then concentrated in vacuo. The resulting crude residue was purified by silica gel column chromotagraphy (ethyl acetate/petroleum ether (1:5)) to give the title product was a yellow oil (0.8 g; yield=58percent). 1H NMR (300 MHz, CDCl3) δ; 8.05 (dd, J=3.0 Hz, J=1.2 Hz, 1H), 7.55 (dd, J=5.1 Hz, J=1.2 Hz, 1H), 7.32 (m, 1H), 2.55 (s, 3H).
Reference：
[1] Bulletin of the Chemical Society of Japan, 2008, vol. 81, # 3, p. 369 - 372
20
[ 1468-83-3 ]
[ 59227-67-7 ]
Yield
Reaction Conditions
Operation in experiment
37%
With bromine; sodium acetate In acetic acid at 20℃;
To a solution of 3-acetylthiophene (2.52 g, 20 mmol, 1.0 eq.) in HOAc (50 ml) was added NaOAc (2.46 g, 30 mmol, 1.5 eq.) followed by bromine (3.2 g, 20 mmol, 1.0 eq.) dropwise over 30 min. The mixture was allowed to stir at room temperature overnight. Water (150 ml) was added and the reaction mixture was stirred for 2 h. The resulting solid was collected by filtration, rinsed with water (10 ml) and PE (20 ml) and dried to afford 8i-2 as a brown solid (1.52 g, yield 37percent).
37%
at 20℃;
Compound 19-2 (0426) To a solution of 3-acetylthiophene (2.52 g, 20 mmol, 1.0 eq) in HOAc (50 mL) was added NaOAc (2.46 g, 30 mmol, 1.5 eq) followed by bromine (3.2 g, 20 mmol, 1.0 eq) dropwise over 30 min. The mixture was allowed to stir at rt overnight. Water (150 mL) was added and the reaction mixture was stirred for 2 h. The resulting solid was collected by filtration, rinsed with water (10 mL) and PE (20 mL) and dried to afford 19-2 as a brown solid (1.52 g, yield 37percent).
Reference：
[1] Indian Journal of Chemistry, Section A: Inorganic, Physical, Theoretical & Analytical, 1988, vol. 27, # 6, p. 538 - 539
22
[ 1468-83-3 ]
[ 105-58-8 ]
[ 53090-46-3 ]
Yield
Reaction Conditions
Operation in experiment
47%
Stage #1: With sodium hydride In toluene for 0.5 h; Heating / reflux Stage #2: With acetic acid In toluene at 0℃;
Example 1B10 11 12(wherein R1 is remaining moiety of the QA group, and R2 is the remaining moiety of the QB group in formula 1.0)Part A:To a mixture containing sodium hydride (18.6 g, 465 mmol) (60percent dispersion in mineral oil, washed with hexane to remove mineral oil) and diethyl carbonate (36 mL, 296 mmol) in toluene (200 mL) at reflux, was added 3-acetylthiophene (3) (18.7 g, 148 mmol) in toluene (60 mL) via dropwise addition using an addition funnel. After the addition was complete, the mixture was refluxed for an additional 30 minutes. The reaction mixture was then cooled to room temperature and placed in an ice bath, quenched with acetic acid (42 mL), water, and extracted with toluene. The combined toluene extracts were washed with water (x4), and brine, dried over magnesium sulfate and concentrated to give a brown oil which was subjected to vacuum distillation. The fraction boiling at approximately 1400C afforded compound 4 (13.8 g, 47 percent yield).
765 mg
Stage #1: With potassium <i>tert</i>-butylate In toluene at 65 - 80℃; for 0.5 h; Inert atmosphere Stage #2: at 80℃; for 1.5 h;
In nitrogen atmosphere, diethyl carbonate 2.3 g of toluene 10 ml solution heated to 65 °C, addingtertButoxy potassium 875 mg, in the 65 °C stirring for 30 minutes. Raising the temperature to 80 °C after, dropping the 3 - acetyl thiophene 618 mg dissolved in toluene 5 ml of liquid, in the 80 °C stirring for 1.5 hours. Adding methanol to the room temperature, adding ethyl acetate, water, saturated salt water are successively washing, magnesium sulfate for drying. The resulting residue is purified by silica gel column chromatography, to obtain the title compound 765 mg.
4.2 g
Stage #1: With potassium <i>tert</i>-butylate In toluene at 60 - 65℃; for 0.5 h; Stage #2: at 75 - 80℃; for 1.5 h;
Diethyl carbonate (9.36 g, 79.37 mmol) in toluene (50 ml) was heated to 60 °C. At thistemperature, potassium t-butoxide (7.11 g, 63.52 mmol) was added portionwise. Theresultant mixture was heated at 65 °C for half an hour. Then the reaction temperature wasraised to 75 °C, and 1-(thiophen-3-yl)ethanone (5 g, 39.7 mmol) was added dropwise. Thereaction mixture was heated to 80 °C for 90 min, and then allowed to cooled to roomtemperature. The precipitate solid was filtrated and washed thoroughly with ether. This solidwas dissolved in ethyl acetate, washed with brine, dried over Na2S04, filtered, andconcentrated under reduced pressure. The residue was purified by silica gel columnchromatography, eluting with PE/Et0Ac=5:1, to get the desired compound (4.2 g) as abrown oil. LC-MS (ESI+): m/z 199.0 (M+Ht
Reference：
[1] Patent: WO2008/82490, 2008, A2, . Location in patent: Page/Page column 71
[2] Journal of Medicinal Chemistry, 1999, vol. 42, # 20, p. 4081 - 4087
[3] Organic Letters, 2016, vol. 18, # 20, p. 5408 - 5411
[4] Patent: CN108137513, 2018, A, . Location in patent: Paragraph 0173; 0174
[5] Patent: WO2018/125983, 2018, A1, . Location in patent: Page/Page column 67; 68
23
[ 1468-83-3 ]
[ 53090-46-3 ]
Yield
Reaction Conditions
Operation in experiment
83%
Stage #1: With potassium <i>tert</i>-butylate In toluene at 60 - 65℃; for 0.5 h; Stage #2: at 75 - 80℃; for 1.5 h;
PREPARATION 22; Ethyl 3-oxo-3-(3-thienyl)propionate; Diethyl carbonate (36.3 ml, 300 mmol) in toluene (18 ml) was heated to 60°C. At this temperature, potassium tert-butoxide (13.0 g, 120 mmol) was portionwise added and, once the addition was over, heated at 65°C for half an hour. Then the temperature is rawased to 75°C and 3-acethylthiophene (9.2g, 73 mmol) in toluene (18 ml) was dropwise added. The reaction mixture was heated at 80°C for 90 min, then allowed to reach room temperature and the precipitated solid was filtrated and washed thoroughly with ether. This solid was dissolved in water. After successive extractions with ethyl acetate, the organic phase was washed with brine and dried over sodium sulfate, filtered and evaporated. A dark oil was obtained (12.0 g, 83percent yield) as the desired final product. No. (CDCl3): 1.25 (t, 3H), 3.90 (s, 2H), 4.20 (q, 2H), 7.35 (m, 1H), 7.55 (m, 1H), 8.10 (m, 1H).
With toluene-4-sulfonic acid In toluene for 24h; Heating / reflux;
1.A
Step A: 3-(2,5,5-trimethyl-l,3-dioxan-2-yl) thiophene; To a mechanical stirred solution of 3-acetyl thiophene (90 g, 0.714 moles) in toluene (1800ml) was added 2,2-dimethyl 1,3-propanediol (222.8 g, 2.143 moles) and p- toluenesulfonic acid monohydrate (0.15 g). The mixture was heated to reflux for 24 hours with water removal using Dean stark trap. The mixture was allowed to cool to 80°C and anhydrous potassium carbonate (9 g) was added followed by saturated solution of sodium bicarbonate (450 ml). The organic phase was separated and aqueous phase extracted by toluene (450 ml). The combined organic phase was washed with saturated sodium chloride solution (450 ml). The organic phase was dried over anhydrous sodium sulfate and evaporated under reduced pressure to yield the desired compound (150 g, 99%) as a pale yellow liquid. This compound was used in the next step without further purification.
99%
With toluene-4-sulfonic acid In toluene for 24h; Reflux; Dean Stark;
1.A
Step A: 3-(2,5,5-trimethyl-1,3-dioxan-2-yl) thiophene To a mechanical stirred solution of 3-acetyl thiophene (90 g, 0.714 moles) in toluene (1800 ml) was added 2,2-dimethyl 1,3-propanediol (222.8 g, 2.143 moles) and p-toluenesulfonic acid monohydrate (0.15 g). The mixture was heated to reflux for 24 hours with water removal using Dean stark trap. The mixture was allowed to cool to 80° C. and anhydrous potassium carbonate (9 g) was added followed by saturated solution of sodium bicarbonate (450 ml). The organic phase was separated and aqueous phase extracted by toluene (450 ml). The combined organic phase was washed with saturated sodium chloride solution (450 ml). The organic phase was dried over anhydrous sodium sulfate and evaporated under reduced pressure to yield the desired compound (150 g, 99%) as a pale yellow liquid. This compound was used in the next step without further purification.
93%
With toluene-4-sulfonic acid In toluene for 36h; Reflux;
1.3
2,5,5-Trimethyl-2-(thiophen-3-yl)-1,3-dioxane: 2,2-Dimethylpropane-1,3-diol (151 g, 1.45 mol, 3.00 equiv.) and p-toluenesulfonic acid (1.2 g) were added to a solution of 1-(thiophen-3-yl)ethanone (61 g, 484.13 mmol, 1.00 equiv.) in toluene (100 mL). The resulting solution was heated at reflux for about 36 hours with azetropic water removal. The reaction mixture was cooled to ambient temperature and then filtered. The filtrate was concentrated in vacuo, and the resulting crude residue was purified by silica gel column chromotagraphy (ethyl acetate/petroleum ether (1:50)) to give the title product as a yellow oil (95 g; yield=93%). 1H NMR (300 MHz, CDCl3) δ: 7.31 (dd, J=3.0 Hz, J=1.2 Hz, 1H), dd, J=5.1 Hz, J=1.2 Hz, 1H), 7.02 (m, 1H), 3.45 (s, 4H), 1.57 (s, 3H), 1.23 (s, 3H), 0.62 (s, 3H).
Example 1B10 11 12(wherein R1 is remaining moiety of the QA group, and R2 is the remaining moiety of the QB group in formula 1.0)Part A:To a mixture containing sodium hydride (18.6 g, 465 mmol) (60% dispersion in mineral oil, washed with hexane to remove mineral oil) and diethyl carbonate (36 mL, 296 mmol) in toluene (200 mL) at reflux, was added 3-acetylthiophene (3) (18.7 g, 148 mmol) in toluene (60 mL) via dropwise addition using an addition funnel. After the addition was complete, the mixture was refluxed for an additional 30 minutes. The reaction mixture was then cooled to room temperature and placed in an ice bath, quenched with acetic acid (42 mL), water, and extracted with toluene. The combined toluene extracts were washed with water (x4), and brine, dried over magnesium sulfate and concentrated to give a brown oil which was subjected to vacuum distillation. The fraction boiling at approximately 1400C afforded compound 4 (13.8 g, 47 % yield).
765 mg
In nitrogen atmosphere, diethyl carbonate 2.3 g of toluene 10 ml solution heated to 65 C, addingtertButoxy potassium 875 mg, in the 65 C stirring for 30 minutes. Raising the temperature to 80 C after, dropping the 3 - acetyl thiophene 618 mg dissolved in toluene 5 ml of liquid, in the 80 C stirring for 1.5 hours. Adding methanol to the room temperature, adding ethyl acetate, water, saturated salt water are successively washing, magnesium sulfate for drying. The resulting residue is purified by silica gel column chromatography, to obtain the title compound 765 mg.
4.2 g
Diethyl carbonate (9.36 g, 79.37 mmol) in toluene (50 ml) was heated to 60 C. At thistemperature, potassium t-butoxide (7.11 g, 63.52 mmol) was added portionwise. Theresultant mixture was heated at 65 C for half an hour. Then the reaction temperature wasraised to 75 C, and 1-(thiophen-3-yl)ethanone (5 g, 39.7 mmol) was added dropwise. Thereaction mixture was heated to 80 C for 90 min, and then allowed to cooled to roomtemperature. The precipitate solid was filtrated and washed thoroughly with ether. This solidwas dissolved in ethyl acetate, washed with brine, dried over Na2S04, filtered, andconcentrated under reduced pressure. The residue was purified by silica gel columnchromatography, eluting with PE/Et0Ac=5:1, to get the desired compound (4.2 g) as abrown oil. LC-MS (ESI+): m/z 199.0 (M+Ht
Preparation 8 1-Thiophen-3-yl-ethylamine The synthetic procedure used in this preparation is outlined below in Scheme J. To a solution of 3-Acetylthiophene (2.0 g, 15.85 mmol) and ammonium acetate (12.2 g, 158.5 mmol) in methanol (50 mL) was added sodium cyanoborohydride (0.7 g, 11.1 mmol) in one portion. The reaction mixture was stirred overnight at room temperature. After removal of methanol, water (20 mL) was added to the residue and the resulting solution was basified by addition of sodium hydroxide to pH=13. The aqueous solution was extracted with dicholromethane and the combined organic phase was dried over sodium sulfate. Removal of the solvent under reduced pressure afforded 1.5 g 1-thiophen-3-yl-ethylamine, yield: 75%. MS (M+H)=128.
75%
Preparation 7: l-Thiophen-3-yl-ethylamine; The synthetic procedure used in this preparation is outlined below in Scheme I. To a solution of 3-Acetylthiophene (2.0 g, 15.85 mmol) and ammonium acetate (12.2 g, 158.5 mmol) in methanol (50 mL) was added sodium cyanoborohydride (0.7 g, 1 l.lmmol) in one portion. The reaction mixture was stirred overnight at RT. After removal of methanol, water (20 mL) was added to the residue and the resulting solution was basified by addition of sodium hydroxide to pH =13. The aqueous solution was ex- EPO <DP n="63"/>tracted with dichloromethane and the combined organic phase was dried over sodium sulfate. Removal of the solvent under reduced pressure afforded 1.5 g l-thiophen-3-yl- ethylamine, yield: 75%. MS (M+H) = 128.
75%
The synthetic procedure used in this preparation is outlined below in Scheme I. To a solution of 3-Acetylthiophene (2.0 g, 15.85 mmol) and ammonium acetate (12.2 g, 158.5 mmol) in methanol (50 mL) was added sodium cyanoborohydride (0.7 g, 11.1 mmol) in one portion. The reaction mixture was stirred overnight at room temperature. After removal of methanol, water (20 mL) was added to the residue and the resulting solution was basified by addition of sodium hydroxide to pH=13. The aqueous solution was extracted with dicholromethane and the combined organic phase was dried over sodium sulfate. Removal of the solvent under reduced pressure afforded 1.5 g 1-thiophen-3-yl-ethylamine, yield: 75%. MS (M+H)=128.
75%
With ammonium acetate; sodium cyanoborohydride; In methanol; at 20.0℃;
Preparation 8 1-Thiophen-3-yl-ethylamine The synthetic procedure used in this preparation is outlined below in Scheme J. 3-Acetylthiophene (2.0 g, 15.85 mmol) and ammonium acetate (12.2 g, 158.5 mmol) in methanol (50 mL) was added sodium cyanoborohydride (0.7 g, 11.1 mmol) in one portion. The reaction mixture was stirred overnight at room temperature. After removal of methanol, water (20 mL) was added to the residue and the resulting solution was basified by addition of sodium hydroxide to pH=13. The aqueous solution was extracted with dichloromethane and the combined organic phase was dried over sodium sulfate. Removal of the solvent under reduced pressure afforded 1.5 g 1-thiophen-3-yl-ethylamine, yield: 75%. MS (M+H)=128.
With ammonium acetate; sodium cyanoborohydride; In methanol; at 20.0℃; for 16.0h;
Step 1. To a solution of compound 3-1 (2 g, 15.9 mmol) in MeOH (20 mL) was added NH4OAc (12.2 g, 0.159 mol) and NaBH3CN (3.5 g, 55.5 mmol) at 20C. After the mixture was stirred at 20C for 16 h, it was concentrated. The residual was partitioned between EtOAc (50 mL) and NaOH solution (5 M, 5 mL) (adjust pH>13). The organic layer was washed with brine (20 mLx2), concentrated and purified by column (20 %-30 % MeOH in DCM) to give the crude compound 3-2 (800 mg, 40% yield). lH NMR (400 MHz, DMSO-/ ) delta 7.63 - 7.61 (d, J= 8.0 Hz, 1 H), 7.58 - 5.57 (m, 1 H), 7.25 - 7.23 (d, J= 8.0 Hz , 2 H), 4.53 - 4.48 (m, 1 H), 1.51 - 1.49 (d, J= 8.0 Hz , 3 H).
PREPARATION 22; Ethyl 3-oxo-3-(3-thienyl)propionate; Diethyl carbonate (36.3 ml, 300 mmol) in toluene (18 ml) was heated to 60C. At this temperature, potassium tert-butoxide (13.0 g, 120 mmol) was portionwise added and, once the addition was over, heated at 65C for half an hour. Then the temperature is rawased to 75C and 3-acethylthiophene (9.2g, 73 mmol) in toluene (18 ml) was dropwise added. The reaction mixture was heated at 80C for 90 min, then allowed to reach room temperature and the precipitated solid was filtrated and washed thoroughly with ether. This solid was dissolved in water. After successive extractions with ethyl acetate, the organic phase was washed with brine and dried over sodium sulfate, filtered and evaporated. A dark oil was obtained (12.0 g, 83% yield) as the desired final product. No. (CDCl3): 1.25 (t, 3H), 3.90 (s, 2H), 4.20 (q, 2H), 7.35 (m, 1H), 7.55 (m, 1H), 8.10 (m, 1H).
Stage #1: 1-(thiophen-3-yl)-ethanone; (E)-3-(dimethylamino)-1-(pyridin-4-yl)prop-2-en-1-one With potassium <i>tert</i>-butylate In tetrahydrofuran at 20℃; for 14h;
Stage #2: With ammonium acetate; acetic acid In tetrahydrofuran Further stages.;
With boron trifluoride diethyl etherate; In tetrahydrofuran; at 65℃; for 16h;
1-(Thiophen-3-yl)ethanone: (E)-4-(Dimethylamino)but-3-en-2-one (1.5 g, 12.6 mmol, 2.00 equiv.) and boron trifluoride-diethyl etherate (1.8 g, 12.4 mmol, 2.00 equiv.) were added to a solution of 1,4-dithiane-2,5-diol (1 g, 6.51 mmol, 1.00 equiv.) in tetrahydrofuran (50 mL). The resulting solution was stirred at about 65 C. for about 16 hours, and then concentrated in vacuo. The resulting crude residue was purified by silica gel column chromotagraphy (ethyl acetate/petroleum ether (1:5)) to give the title product was a yellow oil (0.8 g; yield=58%). 1H NMR (300 MHz, CDCl3) delta; 8.05 (dd, J=3.0 Hz, J=1.2 Hz, 1H), 7.55 (dd, J=5.1 Hz, J=1.2 Hz, 1H), 7.32 (m, 1H), 2.55 (s, 3H).
2.2. Synthesis of indole chalcone derivatives
General procedure: In an RB flask, 1H-indole-3-carboxaldehyde (1 mmol) andappropriate acetophenones (1.2 mmol) were taken and 5 ml ofethanol and 5 drops of piperidine were added. The resulting solutionwas then refluxed at 70 °C and TLC was used to track the reactionprogress. Upon accomplishement of the reaction, thereaction mixture was transferred into cold water and furtherneutralized utilizing 1 N hydrochloric acid. The crude precipitateformed was filtered out, dried and recrystallized from chloroform.All the indole chalcones (1 to 25) were characterized using spectraltechniques and the spectral data are listed in the supplementarydata.
2-[4-methoxy-3-(3-methoxypropoxy)phenyl]-1-(3-thienyl)ethanone[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
6.8 g
With tris-(dibenzylideneacetone)dipalladium(0); 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene; sodium t-butanolate In tetrahydrofuran at 100℃; for 1h;
2.1 Preparation of 2-[4-methoxy-3-(3-methoxypropoxy)phenyl]-1-(3- thienyl)ethanone
A mixture of 4-bromo- l-methoxy-2-(3-methoxypropoxy)benzene (16.5 g, 60 mmol), l-(3- thienyl)ethanone (9.84 g, 78 mmol), i-BuONa (8.64 g, 90 mmol), Xantphos (1.39 g, 2.4 mmol) and Pd2(dba)3 (1.1 g, 1.2 mmol) in THF (200 mL) was heated at 100 °C for 1 hr. After being cooled to rt, the mixture was filtered. The filtrate was concentrated under reduced pressure and the residue was purified by the flash column chromatography to afford 2-[4-methoxy-3-(3- methoxypropoxy)phenyl]- l-(3-thienyl)ethanone (6.8 g) as a brown oil.
A Schlenk tube was loaded with a magnetic stirrer, 2.0 g(15.5 mmol) of 3-acetylthiophene 98%, 2.02 g (15.8 mmol) ofpotassium tert-butoxide 95% and 30 mL of dry THF. After 30 minof stirring at r. t., ethyl-2-thiophenecarboxylate 95% (2.6 mL,18.4 mmol) in 20 mL of THF was added dropwise to the orangemixture. Stirring was continued for 5 h, after which time the reactionwas quenched by addition of water (10 mL) to dissolve theslurry suspension and 30 mL of 1.0 M aqueous HCl. The resultingsolution was stirred for additional 30 min, and extracted withdiethyl ether (3 20 mL). The extracts were combined, dried overMgSO4 and concentrated under vacuum. The resulting residue waspurified by silica gel chromatography (9/1 hexane/ethyl acetate aseluent). The yellow band was collected and slow evaporation of thesolvents overnight afforded 2.10 g (60% yield) of HL as light yellowcrystalline solid. A suitable single crystal was selected from thiscrop for X-ray diffraction analysis. M. p. 102 C. Anal. Calc. forC11H8O2S2 (236.31 gmol1): C, 55.91; H, 3.41; S, 27.14. Found: C,55.79; H, 3.16; S, 28.75%. FT-IR (KBr, cm1): 3422 (m) v(OAH),3099 (m), 3084 (m) v(CAH arom), 2924 (m) v(CAH aliph), 1572(vs) v(C'O and C'C), 785 (vs), 720 (m) d(CAH out-of-plane thienylgroup). 1H NMR (300 MHz, (CD3)2CO): d 16.3 (br s, 1 H, OAH),8.37 (dd, JH-H = 3.0, 1.3 Hz, 1 H, H-2 3-Th), 8.08 (dd, JH-H = 3.8,1.2 Hz, 1 H, H-5 2-Th), 7.92 (dd, JH-H = 5.0, 1.1 Hz, 1 H, H-4 2-Th),7.72 (dd, JH-H = 5.0, 1.3 Hz, 1 H, H-4 3-Th), 7.63 (dd, JH-H = 5.1,3.0 Hz, 1 H, H-5 3-Th), 7.27 (dd, JH-H = 5.0, 3.9 Hz, 1 H, H-3 2-Th),6.99 (s, 1 H, CHC). 13C NMR (75.48 MHz, (CD3)2CO): d 183.3(CO), 176.2 (CHC), 142.2 (C-3 3-Th), 137.9 (C-2 2-Th), 133.5(C-3 2-Th), 131.1 (C-5 2-Th), 129.9 (C-2 3Th), 128
With chloro[1,3-bis(2,6-di-i-propylphenyl)imidazol-2-ylidene]copper(I); dimethyl sulfoxide; potassium hydroxide In toluene at 20℃; for 6h;
81%
With C24H22N6Ni; potassium <i>tert</i>-butylate In toluene at 80℃; for 10h;
79%
With C18H11Cl3CuN4; sodium hydroxide In toluene at 85℃; for 18h;
78%
With silver; potassium hydroxide In toluene at 80℃; for 24h;
General experimental procedure for synthesis of substituted quinolines (4a-4s)
General procedure: To a solution of compound 2-aminobenzyl alcohol (250 mg, 1eq) in Toluene (5 ml) was added acetyl derivatives (1.5 eq) followed by addition of potassium hydroxide (2 eq) and Ag nanoparticles (0.05 eq). Whole reaction mass was heated at 80 °C for 24 h. Progress of the reaction was monitored by TLC. After completion of the reaction, as confirmed by TLC, the reaction mass was brought to room temperature and quenched with water. Ethyl acetate/water work up was done. Organic layer was separated and the aqueous layer was once again extracted with ethyl acetate. All the organic layers were combinedand dried over Na2SO4 and concentrated under reduced pressure to obtain crude material, which was purified by column chromatography to obtain desired material using ethyl acetate/hexane as a mobile phase. Formation of the desired product was confirmed by 1H NMR, 13C NMR, and electron ionization mass spectra.
76%
With (6,8,15,17-tetramethyl-7H,16H-5,9,14,18-tetraaza-dibenzo[b,i]-cyclotetradecenato(2-)-k(4)-N,N',N'',N''')nickel(II); potassium <i>tert</i>-butylate In toluene at 90℃; Inert atmosphere; Schlenk technique; Sealed tube; Green chemistry;
1-(5-amino-1-phenyl-1H-pyrazol-4-yl)-2-(thiophen-3-yl)ethane-1,2-dione[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
62%
With copper(l) iodide; iron(III) chloride hexahydrate; In dimethyl sulfoxide; at 120℃; for 11h;
General procedure: 3-methyl-1-phenyl-1H-pyrazol-5-amine (1 mmol, 173 mg) and acetophenone (1.5 mmol, 180 mg), CuI (10 mol %, 19 mg) and FeCl3.6H2O (10 mol %, 27 mg) were added in DMSO (2 mL) at 120C in a round-bottom flask equipped with a magnetic stirring bar and a reflux condenser. After completion of the reaction the organic mixture was extracted with ethyl acetate (3x50 mL) and then washed with brine solution. The organic fraction was dried with anhydrous sodium sulphate and concentrated in rotavapor under vacuum. The product was purified by column chromatography using silica gel (100-200 mesh, ethyl acetate/hexane as eluent).
1-(2-(adamantan-1-yl)thiophen-3-yl)ethan-1-one[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
84%
With tris(2-phenylpyridinato-N,C2′)iridium(III) In dimethyl sulfoxide Irradiation;
General Procedure for the Syntheses of Alkylated Heteroarenes (1-39).
General procedure: In a 4 mL oven-driedvial, redox-active ester (0.2 mmol, 1.0 equiv.), photocatalyst Ir(ppy)3(0.5 mol%), heteroarene (2.0mmol, 10.0 equiv.) were added to degassed DMSO (2 mL). The mixture was stirred overnight (12-24 h) at room temperature under two 25W white LED irradiation. The reaction process wasmonitored by thin layer chromatography (TLC). After redox-active ester was consumed, themixture was quenched with water, extracted three times with ethyl acetate, and concentrated invacuo. Purification of the crude products by silica gel column chromatography (eluent: PE/EA orPE/DCM) gave the desired products.
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