Name: 531-59-9|7-Methoxy-2H-chromen-2-one|97%
Brand: Ambeed
SKU: A571905
Price: 5.0 USD
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1
[ 93-35-6 ]
[ 77-78-1 ]
[ 531-59-9 ]

Yield	Reaction Conditions	Operation in experiment
95%		General procedure: 0.4g of SM1 (2.2mmol), SM2 (2.4mmol) and SM3 (2.2mmol), respectively, were dissolved with CH3CN (2.0mL). After that, solid KOH (1.5 or 3 equivalents) was added, and stirred during thirty minutes. 2.1 equivalents of dimethyl sulfate (Me2SO4) were added to the mixture and heating for 48h at 40C. Finally, when reaction was completed (monitored by TLC analysis), the solid was filtered off and dried to afford the corresponding compounds 1 (6,7-dimethoxy-2H-chromen-2-one), 7 (7-methoxy-2H-chromen-2-one) and 13 (7-methoxy-4-methyl-2H-chromen-2-one), respectively.
90.2%	With potassium carbonate; potassium iodide; In acetone; at 20℃; for 5h;	General procedure: As an example, to a solution of 7-hydroxycoumarin (1.16 g, 7.15 mmol) in acetone (50 mL) was added K2CO3 (2.01 g, 14.55 mmol) and KI (4.38 g, 26.39 mmol) at room temperature. After stirring at room temperature for 10 min, 3-chloropropene (0.90 mL, 11.05 mmol) was added to the reaction mixture, and whole was refluxed at 60 C for 22 h. The solid was separated from the mixture, washed with acetone. Then the mixture was filtered, and the filtrate was washed by acetone (50 mL) three times. Acetone phase was combined, and then evaporated under reduced pressure. The residue was recrystallized in Petroleum ether-ethyl acetate (1:1, V/V) to produce a white needle shaped crystallite (1.31 g). Yield 90.6%.

Reference： [1]European Journal of Medicinal Chemistry,2014,vol. 77,p. 400 - 408
[2]European Journal of Medicinal Chemistry,2012,vol. 54,p. 582 - 590
[3]Indian Journal of Chemistry - Section B Organic and Medicinal Chemistry,2000,vol. 39,p. 387 - 389
[4]European Journal of Medicinal Chemistry,2009,vol. 44,p. 2252 - 2259
[5]Journal of the Indian Chemical Society,1935,vol. 12,p. 140

2
[ 93-35-6 ]
[ 74-88-4 ]
[ 531-59-9 ]

Yield	Reaction Conditions	Operation in experiment
97%	With potassium carbonate; In acetone; at 25℃; for 5h;Inert atmosphere;	K2CO3 (2.0 g, 14.5 mmol) and MeI (3.42 g, 24.1 mmol) were added to a solution of 7-hydroxyl coumarin (6) (2.0 g, 12.3 mmol) in acetone (100 mL) and the mixture was reacted for 5 h. After filtration and dilution with EtOAc, the resulting solution was washed with brine and dried over anhydrous Na2SO4. The solvent was removed to afford compound 10 (2.1 g, 97%) as a crystalline solid. 1H NMR (400 MHz, CDCl3) delta 7.95 (d, J = 16.1 Hz, 1H), 7.40 (d, J = 8.7 Hz, 1H), 6.53-6.48 (m, 2H), 6.38 (s, 1H), 3.81 (s, 3H).
73%		The 7-hydroxy-coumarin (1g, 6.2mmol) with 30 ml acetone dissolved, adding anhydrous potassium carbonate (1.7g, 12 . 35mmol), stirring the mixture at room temperature for 10 min. Add iodomethane (1.05g, 7 . 41mmol), heating reflux reaction 5h, stop heating, hot filtering, the filtrate is turns on lathe does, ethanol re-crystallization of the white crystal 0.8g, yield 73%.

Reference： [1]Tetrahedron,1992,vol. 48,p. 4239 - 4246
[2]European Journal of Medicinal Chemistry,2016,vol. 122,p. 674 - 683
[3]ACS Medicinal Chemistry Letters,2012,vol. 3,p. 327 - 331
[4]Chemistry - An Asian Journal,2012,vol. 7,p. 1616 - 1623
[5]Patent: CN103319465,2016,B .Location in patent: Paragraph 0048-0048
[6]Tetrahedron Letters,1985,vol. 26,p. 4677 - 4680
[7]Journal Of Scientific and Industrial Research,1957,vol. 16B,p. 257,260
Chem.Abstr.,1958,p. 376
[8]Bulletin de la Classe des Sciences, Academie Royale de Belgique,1953,vol. <5> 39,p. 1064,1074
[9]Chemical and pharmaceutical bulletin,1989,vol. 37,p. 1957 - 1959
[10]Australian Journal of Chemistry,1989,vol. 42,p. 1235 - 1248
[11]Egyptian Journal of Chemistry,2008,vol. 51,p. 107 - 114
[12]Organic and Biomolecular Chemistry,2018,vol. 16,p. 3396 - 3401

3
[ 531-59-9 ]
[ 72167-80-7 ]

Yield	Reaction Conditions	Operation in experiment
99.5%	With N-chloro-succinimide; copper(II) chloride monohydrate; zinc(II) chloride; In acetonitrile; at 82℃; for 0.0833333h;	General procedure: To a 50 mL flask, the coumarin (1 mmol), appropriate amount of NXS, the Lewisacid catalyst and 20 mL anhydrous solvent were added in. The mixture was heated toreflux with a condenser under the protection of a drying tube. The reaction progresswas monitored by TLC. When the reaction was completed, the mixture was cooled toroom temperature. The solvent was removed by vacuum rotary evaporation, and theresidue was dispensed in 25 mL 5% sodium hydrogen sulfite (NaHSO3) aqueoussolution and then extracted with 25 mL ethyl acetate (EtOAc) for three times. Theorganic layer was combined, washed with 10 mL water and dried over anhydroussodium sulphate (Na2SO4). After the solvent was removed, the crude product waspurified by silica gel (300-400 mesh) column chromatograph.
80%	With N-Bromosuccinimide; In acetonitrile; at 80℃; for 0.0833333h;Microwave irradiation;	General procedure: 4-Methyl-6,7-dimethoxycoumarin (0.05 g, 0.227 mmol) was dissolved in acetonitrile (5 ml) in a microwave vessel. N-Bromosuccinimide (0.06 g, 0.340 mmol) was added to the mixture and the vessel inserted into the microwave at 250 W for 5 min at 80 C. The reaction was monitored by thin layer chromatography (silica gel, 3:1 CH2Cl2/EtOAc). Upon completion, the reaction mixture was cooled and the resultant precipitate was collected by vacuum filtration. The crude product was then recrystallized from a mixture of CH2Cl2/MeOH to yield 3-bromo-4-methyl-6,7-dimethoxycoumarin (1a, 0.060 g, 89%)
80%	With N-Bromosuccinimide; ammonium acetate; In acetonitrile; at 20℃; for 10h;Inert atmosphere;	Under a nitrogen atmosphere, a solution containing <strong>[531-59-9]7-methoxycoumarin</strong> (5.00 g, 28.40 mmol) in acetonitrile (50 mL)N-bromosuccinimide (7.61 g, 42.61 mmol) and ammonium acetate (0.22 g, 2.84 mmol) were added and the mixture was stirred at room temperature for 10 hours. After completion of the reaction, the mixture was extracted with ethyl acetate (3 x 100 mL), saturated brine and water, and the organic layer was washed with anhydrousDried sodium sulfate, evaporated to dryness and separated by silica gel column chromatography (eluent: dichloromethane / petroleum ether, 2: 1,500 ml) to give the white product (5.79 g, 80.0% yield).

56%

With N-Bromosuccinimide; In N,N-dimethyl-formamide; at 75℃; for 6h;

General procedure: A general procedure for preparation of compounds 5, 9a-b and13: the corresponding N-bromosuccinimide (1.2 equiv) was addedslowly to a solution of <strong>[531-59-9]7-methoxycoumarin</strong> (1 equiv) and sodiumacetate (0.05 equiv) in DMF, and the mixture was stirred at 75 Cfor 6 h. After pouring into brine, and washing, then mixture wasextracted with ethyl acetate. The combined organic layers werewashed with brine, dried over anhydrous Na2SO4 and then filteredand concentrated in vacuum. The product was purified by columnchromatography (0-20% ethyl acetate in petroleum ether).

Reference： [1]Synlett,2019,vol. 30,p. 630 - 634
[2]Cell Chemical Biology,2020,vol. 27,p. 334 - 349
[3]ACS Medicinal Chemistry Letters,2012,vol. 3,p. 327 - 331
[4]Canadian Journal of Chemistry,2013,vol. 91,p. 1155 - 1159
[5]Tetrahedron Letters,2012,vol. 53,p. 3319 - 3321
[6]Patent: CN106967027,2017,A .Location in patent: Paragraph 0045; 0047
[7]Bioorganic and Medicinal Chemistry,2017,vol. 25,p. 3531 - 3539
[8]Chemische Berichte,1942,vol. 75,p. 971,974
[9]Dyes and Pigments,2014,vol. 107,p. 45 - 50
[10]Organic and biomolecular chemistry,2019,vol. 17,p. 186 - 194

4
[ 531-59-9 ]
[ 20921-02-2 ]

Yield	Reaction Conditions	Operation in experiment
96%	palladium-carbon;	Preparation of 7-Methoxy-chroman-2-one (Compound 14A) Compound 14A was prepared by hydrogenation of <strong>[531-59-9]7-methoxy-chromen-2-one</strong> catalyzed by 10% Pd/C in 96% yield. MS: 179 (M+1)+.

Reference： [1]Tetrahedron Letters,2006,vol. 47,p. 5807 - 5810
[2]Patent: US2003/207915,2003,A1
[3]Australian Journal of Chemistry,1989,vol. 42,p. 1235 - 1248

5
[ 531-59-9 ]
[ 300767-53-7 ]

Reference： [1]Tetrahedron Letters,2009,vol. 50,p. 413 - 415
[2]Chemical and Pharmaceutical Bulletin,2000,vol. 48,p. 1138 - 1147
[3]Chemical and Pharmaceutical Bulletin,1982,vol. 30,p. 2036 - 2044

6
[ 150-19-6 ]
[ 471-25-0 ]
[ 531-59-9 ]
[ 51559-36-5 ]

Yield	Reaction Conditions	Operation in experiment
47%; 11%	With trifluoroacetic acid; In chlorobenzene; at 100℃; for 1h;Inert atmosphere;	General procedure: A mixture of Phenol derivatives (1) (1.0 mmol), trifluoromethanesulfonic acid (1.0 mmol) and propiolic acid (2a) (0.5 mmol) in PhCl (3.0 mL) was stirred at 100 C for 1 h. After completion of reaction as indicated by TLC, the reaction mixture was poured into H2O, neutralized with NaHCO3 solution and extracted CH2Cl2. The organic layer was washed with 2M NaOH, dried over anhydrous MgSO4. The solvent was removed in vaccum, and the products were purified by silica gel columnchromatography (EtOAc-Hex) to give the desired product 3.
47%; 11%	With trifluorormethanesulfonic acid; In chlorobenzene; at 100℃; for 1h;	General procedure: Cresol instead of phenol, and the reaction time was 1 hour, the title compound was synthesized in the same manner as in Example 1. White solid (59 mg, 74%)

Reference： [1]Tetrahedron Letters,2016,vol. 57,p. 3600 - 3603
[2]Patent: KR101656876,2016,B1 .Location in patent: Paragraph 0119; 0120
[3]Tetrahedron,2006,vol. 62,p. 6918 - 6925
[4]Tetrahedron,2006,vol. 62,p. 6918 - 6925
[5]Synthesis,2004,p. 1466 - 1470
[6]Synthesis,2011,p. 1283 - 1289

7
2-formyl-5-methoxyphenyl 2-chloroacetate [ No CAS ]
[ 531-59-9 ]

Yield	Reaction Conditions	Operation in experiment
34%	In N,N-dimethyl-formamide;Electrochemical reaction;	General procedure: A series of controlled-potential electrolyses ofcompounds 1a-5a at a silver gauze cathode was carried out in DMFcontaining 0.10 M TBABF4. Coulometric n values and yields of thedesired coumarins (1b-5b) are compiled in Table II; each entry correspondsto the average of at least duplicate experiments. Tabulatedn values (the number of electrons transferred per molecule of substrate)were accurate to ±0.10. For all substrates, the coulometricn value was slightly higher than 1, supporting a mechanism wherethe carbon-chlorine bond is mainly cleaved in a one-electron processto give a radical intermediate that cyclizes intramolecularly to forma coumarin.

Reference： [1]Journal of the Electrochemical Society,2014,vol. 161,p. G98 - G102
[2]Journal of Chemical Research - Part S,2003,p. 628 - 629

8
[ 673-22-3 ]
[ 21204-67-1 ]
[ 531-59-9 ]

Yield	Reaction Conditions	Operation in experiment
71%	With N,N-diethylaniline; at 210℃; for 2h;	Compound 6 was synthesized following a literature procedure. ADDIN EN.CITE Starevi2011251712517251717tefan StareviBroi, PetraTurk, SamoCesar, JokoRiner, Tea LaninikGobec, StanislavSynthesis and Biological Evaluation of (6- and 7-Phenyl) Coumarin Derivatives as Selective Nonsteroidal Inhibitors of 17beta-Hydroxysteroid Dehydrogenase Type 1Journal of Medicinal ChemistryJournal Of Medicinal ChemistryJ Med ChemJ. Med. Chem.248-6154120111 A mixture of 2-hydroxy-4-methoxybenzaldehyde (1.0 g, 6.58 mmol) and ((methoxycarbonyl)-methylene)triphenylphosphorane (2.75 g, 7.89 mmol) was heated in DMF (65 mL) at 210 C for 2 h. After cooling to room temperature, the reaction mixture was diluted with 5% HCl solution (70 mL) and extracted with ether. The combined organic layers were washed with brine, dried over anhydrous Na2SO4 and then filtered and concentrated in vacuum. The product was purified by column chromatography (0-20% ethyl acetate in petroleum ether). Yield: 822 mg (71%), white solid (mp 111-114 C). 1H NMR (400 MHz, CDCl3) delta 7.60 (d, J = 9.4 Hz, 1H), 7.33 (d, J = 8.6 Hz, 1H), 6.79 (dd, J = 8.6, 2.4 Hz, 1H), 6.73 (d, J = 2.4 Hz, 1H), 6.19 (d, J = 9.5 Hz, 1H), 3.82 (s, 3H). 13C NMR (100 MHz, CDCl3) delta 162.76, 161.16, 155.77, 143.54, 128.83, 112.89, 112.45, 100.75, 55.75.

Reference： [1]European Journal of Organic Chemistry,2017,vol. 2017,p. 5204 - 5213
[2]Bioorganic and Medicinal Chemistry,2017,vol. 25,p. 3531 - 3539
[3]Journal of Medicinal Chemistry,2011,vol. 54,p. 248 - 261

9
[ 17577-28-5 ]
[ 531-59-9 ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 2 steps 1: potassium hydroxide / ethanol / 1.5 h / 80 °C 2: potassium carbonate; potassium iodide / acetone / 5 h / 20 °C

Reference： [1]Liu, Guang-Lu; Hao, Bing; Liu, Shao-Peng; Wang, Gao-Xue [European Journal of Medicinal Chemistry, 2012, vol. 54, p. 582 - 590]

10
[ 531-59-9 ]
[ 1417997-93-3 ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 6 steps 1: 6 h / Inert atmosphere 2: pyridine / dichloromethane / 2 h / 20 °C 3: tetrakis(triphenylphosphine) palladium⁽⁰⁾; potassium carbonate / N,N-dimethyl-formamide / 12 h / 90 °C 4: lithium hydroxide / methanol 5: triethylamine / tetrahydrofuran / 1 h / 20 °C 6: hydroxylamine hydrochloride; potassium hydroxide / methanol / 3 h / 20 °C

Reference： [1]Huang, Wei-Jan; Wang, Yi-Ching; Chao, Shi-Wei; Yang, Chen-Yui; Chen, Liang-Chieh; Lin, Mei-Hsiang; Hou, Wen-Chi; Chen, Mei-Yu; Lee, Tai-Lin; Yang, Ping; Chang, Chung-I [ChemMedChem, 2012, vol. 7, # 10, p. 1815 - 1824]

11
[ 531-59-9 ]
[ 1809-20-7 ]
[ 1499139-80-8 ]

Yield	Reaction Conditions	Operation in experiment
72%	With C17H17Br2N3OPd; silver nitrate; In acetonitrile; at 80℃; for 10h;Schlenk technique; Inert atmosphere;	General procedure: In a typical reaction, a Schlenk tube charged with coumarins (0.5mmol), dialkyl phosphite (1.0mmol), NHC palladium complex, AgNO3 and solvent (2mL) was heated at 80C for 10h. The mixture was then cooled, filtered and the filtrate was evaporated. Purification of the residue by column chromatography (silica, petroleum ether/ethylacetate=2/1-1/4, v/v) produced the pure products, which were characterized by 1H NMR and 13C NMR. The analytical data of the products were shown in the Supporting Information.
64%	With magnesium(II) nitrate hexahydrate; silver nitrate; In acetonitrile; at 100℃; for 6h;Inert atmosphere;	General procedure: In a Schlenk tube, coumarin 1 (0.5mmol), dialkyl H-phosphite 2 (1.0mmol), AgNO3 (0.025mmol, 4.2mg) and Mg(NO3)2·6H2O (0.25mmol, 64mg) were added and charged with Nitrogen (3 cycles). Anhydrous CH3CN (1mL) was then added. After heating in the oil bath at 100C for 6h (monitored by TLC), 5mL ethylacetate was added to dilute the reaction solution. The solution was filtrated, and the solvent was distilled under vacuum. The crude product was purified by silica gel column chromatography to give the desired product 3 using ethylacetate/petroleum ether (1:5 to 2:1) as eluant.
64%	With sodium nitrate; silver nitrate; In methanol; at 90℃; for 5h;	<strong>[531-59-9]7-Methoxycoumarin</strong> (1.0 mmol, 176 mg) and diisopropyl phosphite (2.0 mmol, 232 mg) were added to a 25 mL reaction flask and dissolved in 5.0 mL of methanol,Then AgNO3 (0.05 mmol, 8.4 mg) and NaNO3 (0.5 mmol, 42.5 mg) were added.The reaction was carried out by heating under stirring in an oil bath,The reaction temperature was 90 C.By TLC tracking the reaction process,Reaction time is 5h,After the reaction,The solvent was distilled off under reduced pressure,To the raffinate was added 10 mL of ethyl acetate,Washed twice with 20 mL of saturated NaHCO3,And then washed with 10 mL of saturated brine once,The solution was concentrated and purified by silica gel column chromatography (eluent: ethyl acetate / petroleum ether = 1/3)To give 0.216 g of a white solid,Yield 64.0%.

Reference： [1]Organic Letters,2013,vol. 15,p. 6266 - 6269
[2]Journal of Organometallic Chemistry,2016,vol. 818,p. 179 - 184
[3]Tetrahedron,2015,vol. 71,p. 8178 - 8186
[4]Patent: CN105037428,2017,B .Location in patent: Paragraph 0028; 0029; 0030; 0031

12
[ 531-59-9 ]
[ 2926-29-6 ]
[ 1562426-78-1 ]

Yield	Reaction Conditions	Operation in experiment
67%	With dipotassium hydrogenphosphate; In acetone; at 20℃; for 12h;Inert atmosphere; Irradiation; Green chemistry;	General procedure: To a tube were added 1a (1.0 equiv), CF 3 SO 2 Na(4.0 equiv),K 2 HPO 4 , Acetone (2 mL). Then the tube was evacuated and backlledwith argon for three times. The tube around condensate water wasstirred at room temperature in argon with the irradiation of Xenon lampfor 12 h. After the reaction was nished, the mixture was washed withsaturated sodium chloride solution and then extracted with ethylacetate for three times. The combined organic layers were dried overNa 2 SO 4 and concentrated under reduced pressure, then puried bychromatography on silica gel.

Reference： [1]Journal of Fluorine Chemistry,2018,vol. 214,p. 42 - 47
[2]Organic and Biomolecular Chemistry,2015,vol. 13,p. 10917 - 10922
[3]Chemical Communications,2014,vol. 50,p. 3359 - 3362

13
[ 531-59-9 ]
2-oxo-2-o-tolylacetic acid [ No CAS ]
7-methoxy-3,4-bis-(2-methylbenzoyl)chromen-2-one [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
86%	With dipotassium peroxodisulfate; silver nitrate; In water; dimethyl sulfoxide; at 20℃; for 24h;Inert atmosphere; Schlenk technique; Sealed tube;	General procedure: A 10mL oven-dried Schlenk-tube was charged with AgNO3 (3.4mg, 10mol%), coumarin (1, 0.2mmol, 1.0equiv), and K2S2O8 (108mg, 0.4mmol, 2.0equiv). The tube was evacuated and backfilled with nitrogen (three times). alpha-Oxocarboxylic acids (2, 0.48mmol, 2.4equiv) in DMSO/H2O (1:1) 2mL were added by syringe. The tube was then sealed and the mixture was stirred for 24h at room temperature. Upon completion of the reaction, the mixture was diluted with EtOAc, filtered through a pad of Celite, and the filtrate was then removed under vacuo. The residue was purified with chromatography column on silica gel (gradient eluent of EtOAc/petroleum ether: 1:30 to 1:15) to give the corresponding products 3 or 4 in yields listed in Tables 2 and 3.

Reference： [1]Tetrahedron,2015,vol. 71,p. 630 - 636

14
[ 616-47-7 ]
[ 93-35-6 ]
[ 531-59-9 ]

Yield	Reaction Conditions	Operation in experiment
70%	With Di-tert-butyl acetylenedicarboxylate; In neat (no solvent); at 100℃; for 0.0833333h;Microwave irradiation; Green chemistry;	General procedure: In a 10-mL reaction vial, a mixture of N-methylimidazole (3, 0.26 g, 2.0 mmol) and dimethyl acetylenedicarboxylate (2a, 0.24 mL, 2.0 mmol) under solvent-free condition was stirred for 1 min. Subsequently, 4-hydroxycoumarin (1a, 0.32 g, 2.0 mmol) was added to the reaction mixture, and the reaction vial was capped and pre-stirred for 20 s. The mixture was subjected to microwave irradiation at a power of 600 W for 6 min at 100 C. Upon completion, monitored by TLC, the reaction mixture was cooled to room temperature. The resulting precipitate was separated by filtration and recrystallized from diethyl ether (Et2O) to afford the pure compound 4a.

Reference： [1]Journal of the Serbian Chemical Society,2015,vol. 80,p. 459 - 464

15
[ 93-35-6 ]
[ 762-42-5 ]
[ 531-59-9 ]

Yield	Reaction Conditions	Operation in experiment
98%	With 1-methyl-1H-imidazole; In neat (no solvent); at 100℃; for 0.0666667h;Microwave irradiation; Green chemistry;	General procedure: In a 10-mL reaction vial, a mixture of N-methylimidazole (3, 0.26 g, 2.0 mmol) and dimethyl acetylenedicarboxylate (2a, 0.24 mL, 2.0 mmol) under solvent-free condition was stirred for 1 min. Subsequently, 4-hydroxycoumarin (1a, 0.32 g, 2.0 mmol) was added to the reaction mixture, and the reaction vial was capped and pre-stirred for 20 s. The mixture was subjected to microwave irradiation at a power of 600 W for 6 min at 100 C. Upon completion, monitored by TLC, the reaction mixture was cooled to room temperature. The resulting precipitate was separated by filtration and recrystallized from diethyl ether (Et2O) to afford the pure compound 4a.

Reference： [1]Journal of the Serbian Chemical Society,2015,vol. 80,p. 459 - 464

16
[ 109-99-9 ]
[ 531-59-9 ]
7-methoxy-3-(tetrahydrofuran-2-yl)-2H-chromen-2-one [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
77%	With di-tert-butyl peroxide; copper diacetate; potassium iodide; In tetrahydrofuran; at 100℃; for 24h;Inert atmosphere;	General procedure: 0.6 mmol DTBP in 1.5 mL THF was added into the 10 mL flask charged with 0.2 mmol coumarin, 10 mol % Cu(OAc)2, 20 mol % KI. The reaction mixture was stirred at 100 C for specified hours, then cooled down to room temperature. Filtrate was concentrated under reduced pressure. The residue was purified by chromatography on silica gel (elute: EtOAc/Petroleum ether 1/3-1/10, v/v) to give the desired product.

Reference： [1]Tetrahedron,2015,vol. 71,p. 6689 - 6693
[2]Organic and Biomolecular Chemistry,2018,vol. 16,p. 3396 - 3401
[3]Advanced Synthesis and Catalysis,2016,vol. 358,p. 2422 - 2426

17
[ 646-06-0 ]
[ 531-59-9 ]
3-(1,3-dioxolan-2-yl)-7-methoxy-2H-chromen-2-one [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
87%	With di-tert-butyl peroxide; copper diacetate; potassium iodide; In tetrahydrofuran; at 100℃; for 24h;Inert atmosphere;	General procedure: 0.6 mmol DTBP in 1.5 mL THF was added into the 10 mL flask charged with 0.2 mmol coumarin, 10 mol % Cu(OAc)2, 20 mol % KI. The reaction mixture was stirred at 100 C for specified hours, then cooled down to room temperature. Filtrate was concentrated under reduced pressure. The residue was purified by chromatography on silica gel (elute: EtOAc/Petroleum ether 1/3-1/10, v/v) to give the desired product.

Reference： [1]Tetrahedron,2015,vol. 71,p. 6689 - 6693

18
[ 531-59-9 ]
[ 110-82-7 ]
3-cyclohexyl-7-methoxy-2H-chromen-2-one [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
79%	With di-tert-butyl peroxide; copper(II) bis(trifluoromethanesulfonate); In tetrahydrofuran; at 100℃; for 30h;Inert atmosphere;	General procedure: 0.6 mmol DTBP in 1.5 mL THF was added into the 10 mL flask charged with 0.2 mmol coumarin, 10 mol % Cu(OAc)2, 20 mol % KI. The reaction mixture was stirred at 100 C for specified hours, then cooled down to room temperature. Filtrate was concentrated under reduced pressure. The residue was purified by chromatography on silica gel (elute: EtOAc/Petroleum ether 1/3-1/10, v/v) to give the desired product.

Reference： [1]Tetrahedron,2015,vol. 71,p. 6689 - 6693

19
[ 531-59-9 ]
[ 291-64-5 ]
3-cycloheptyl-7-methoxy-2H-chromen-2-one [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
80%	With di-tert-butyl peroxide; copper(II) bis(trifluoromethanesulfonate); In tetrahydrofuran; at 100℃; for 24h;Inert atmosphere;	General procedure: 0.6 mmol DTBP in 1.5 mL THF was added into the 10 mL flask charged with 0.2 mmol coumarin, 10 mol % Cu(OAc)2, 20 mol % KI. The reaction mixture was stirred at 100 C for specified hours, then cooled down to room temperature. Filtrate was concentrated under reduced pressure. The residue was purified by chromatography on silica gel (elute: EtOAc/Petroleum ether 1/3-1/10, v/v) to give the desired product.

Reference： [1]Tetrahedron,2015,vol. 71,p. 6689 - 6693

20
[ 531-59-9 ]
[ 292-64-8 ]
3-cyclooctyl-7-methoxy-2H-chromen-2-one [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
85%	With di-tert-butyl peroxide; copper(II) bis(trifluoromethanesulfonate); In tetrahydrofuran; at 100℃; for 30h;Inert atmosphere;	General procedure: 0.6 mmol DTBP in 1.5 mL THF was added into the 10 mL flask charged with 0.2 mmol coumarin, 10 mol % Cu(OAc)2, 20 mol % KI. The reaction mixture was stirred at 100 C for specified hours, then cooled down to room temperature. Filtrate was concentrated under reduced pressure. The residue was purified by chromatography on silica gel (elute: EtOAc/Petroleum ether 1/3-1/10, v/v) to give the desired product.

Reference： [1]Tetrahedron,2015,vol. 71,p. 6689 - 6693

21
[ 531-59-9 ]
[ 3278-34-0 ]
ethyl 2-(7-methoxy-2-oxo-2H-chromen-3-yl)acetate [ No CAS ]

Reference： [1]European Journal of Organic Chemistry,2015,vol. 2015,p. 4098 - 4101

22
[ 531-59-9 ]
[ 98-80-6 ]
(S)-7-methoxy-4-phenylchroman-2-one [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
52%		General procedure: Under an atmosphere of argon, [Rh(OH)(cod)]2 (2.7 mg,6.0 lmol) and (S)-BICMAP (8.2 mg, 13.2 lmol) were added to arylboronicacid (4.0 or 2.0 mmol) in 1,4-dioxane (1.0 or 0.5 mL) andwater (0.1 or 0.05 mL). After stirring the mixture for 1 h at roomtemperature, the coumarin derivative (0.40 or 0.20 mmol) wasadded. The reaction mixture was stirred at 60 C for 16 h. Afterbeing cooled to room temperature, the mixture was quenched withsat. NaHCO3 aq and diluted with EtOAc. The organic layer waswashed with water and brine, and dried over Na2SO4. The filtratewas concentrated with a rotary evaporator and the residue waspurified by column chromatography (elution with n-hexane/EtOAc = 10-8/1). 52% yield (26.2 mg, 0.103 mmol), 98% ee; [a]D20 = +41.0 (c 0.37,CHCl3) {lit. [a]D20 = 43.0 (c 1.0, CHCl3) for 99% ee (R)};9 white solid;mp 130-131 C; 1H NMR (CDCl3, 300 MHz) d 2.95-3.11 (m, 2H),3.81 (s, 3H), 4.29 (t, J = 6.9 Hz, 1H), 6.62-6.65 (m, 2H), 6.68-6.88(m, 1H), 7.14-7.16 (m, 2H), 7.26-7.37 (m, 3H); 13C NMR (CDCl3,75 MHz) d 37.3, 40.1, 55.5, 102.5, 110.7, 117.6, 127.5, 127.6,128.9, 129.1, 140.7, 152.5, 160.0, 167.6; EI-MS m/z (rel intensity)254 (M+, 79); HRMS (ESI-orbitrap) m/z calcd for C16H14O3+H255.1016 found 255.1014; HPLC (Daicel CHIRALCEL OD-H, 0.46 / 25 cm, UV 254 nm, hexane/2-propanol = 95:5, 1.0 mL/min)tR = 15.8 min (major) and 19.0 min (minor).

Reference： [1]Tetrahedron Asymmetry,2015,vol. 26,p. 1065 - 1068

23
[ 531-59-9 ]
[ 98-80-6 ]
[ 2555-22-8 ]

Yield	Reaction Conditions	Operation in experiment
85%	With potassium permanganate; acetic acid; In acetonitrile; at 80℃; for 0.5h;	In a 50 mL reaction flaskInto KMnO4 (1.0 mmol, 158 mg) and5 mL of glacial acetic acid,Refluxed at 120 & lt; 0 & gt; C for 20 min;After the solution was returned to room temperature,Was added to the solution5 mL of acetonitrile,Then <strong>[531-59-9]7-methoxycoumarin</strong> (0.5 mmol, 88 mg)And phenylboronic acid (1.0 mmol, 122 mg),The reaction was stirred in an oil bath at 80 C for 0.5 h.After completion of the reaction, the reaction solution was poured into 20 g of an ice-water mixture, and the precipitated solid was stirred. Then, the filter cake was washed with water,The filter cake was dried and recrystallized from ethyl acetate and petroleum ether,0.107 g of a colorless powdery solid was obtained in a yield of 85.0%

Reference： [1]RSC Advances,2016,vol. 6,p. 35936 - 35944
[2]Patent: CN105566270,2016,A .Location in patent: Paragraph 0057-0059

24
[ 531-59-9 ]
[ 124-41-4 ]
C₁₁H₁₂O₄ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
93%	In methanol; for 4.5h;Inert atmosphere; Reflux;	A solution of freshly prepared MeONa [made from Na (1.0 g) and dried methanol (25 mL)] were added to a suspension of 10 (1.0 g, 5.7 mmol) in dry methanol (15 mL) under N2, and the mixture was refluxed for 4.5 h. After cooling and neutralization with 2 N HCl, the mixture was filtered and dried to give 11 (1.1 g, 93%) as a white solid. NH4OH (12.5 mL 25% aq) was added to a solution of 11 (0.6 g, 2.9 mmol) in dioxane (5 mL). Then a solution of iodine (0.79 g, 3.1 mmol) in 25 mL of aqueous KI (5% w/v) was added dropwised with stirring at 0 C. After stirring for 1 h, the mixture was slightly acidified with 2.5 N H2SO4. The mixture was filtered and dried to give the mixture of 12 and 13. Then diphenyl ether (8 mL) was added and the mixture was heated under N2 at 190 C for 4 h. After cooling, the mixture purified by column chromatography on silica gel (Hexane: EA = 9: 1) to afford the desired product 13 (600 mg, 69% for two steps) as a white solid.

Reference： [1]European Journal of Medicinal Chemistry,2016,vol. 122,p. 674 - 683

25
[ 531-59-9 ]
[ 100-63-0 ]
[ 2555-22-8 ]

Yield	Reaction Conditions	Operation in experiment
75%	With potassium permanganate; In acetonitrile; at 80℃; for 3h;Schlenk technique;	General procedure: In a 50 mL Schlenk tube, a solution of coumarins 1 (orquinolinone derivatives 4) (0.5 mmol), arylhydrazines 2(1.0 mmol), and KMnO4 (1.5 mmol, 237 mg) in CH3CN (10mL) was stirred at 80C for 3.0 h. After the reaction wasfinished, the mixture was diluted with saturated NaClsolution (50 mL). Then the aqueous layer was extractedwith EtOAc (3 × 15 mL). The organic phase was dried overanhydrous Na2SO4 and concentrated under vacuum. Thecrude product was purified by silica gel column chromatographyusing ethyl acetate/petroleum ether (1:5 to 2:1) aseluant to obtain the desired product 3 (or 5).

Reference： [1]Zeitschrift fur Naturforschung, B: Chemical Sciences,2016,vol. 71,p. 1115 - 1123

26
[ 531-59-9 ]
[ 114382-26-2 ]

Yield	Reaction Conditions	Operation in experiment
70%	With N-iodo-succinimide; toluene-4-sulfonic acid; In tetrahydrofuran; for 10h;Reflux;	The 7-MC -1 (1g, 5.68mmol), the toluene sulphonic acid (TsOH 0.98 g, 5 . 68mmol) dissolved in 30mLTHF in (tetrahydrofuran), under stirring vigorously, slowly dropping therein 20mLTHF NIS of (N-iodo succinimide 1.5g, 6 . 82mmol) solution. Heating reflux reaction 10h, stop heating, return to room temperature, the solvent turns on lathe does, solid using dichloromethane/petroleum ether = 1:1 column chromatography separation, the white solid obtained 0.12g, yield 70%.

Reference： [1]Patent: CN103319465,2016,B .Location in patent: Paragraph 0050-0051

27
[ 531-59-9 ]
[ 4559-70-0 ]
trans-3,4-bis(diphenylphosphoryl)-7-methoxychroman-2-one [ No CAS ]

Reference： [1]Organic Letters,2017,vol. 19,p. 1394 - 1397

28
[ 531-59-9 ]
[ 4559-70-0 ]
3-(diphenylphosphoryl)-7-methoxy-2H-chromen-2-one [ No CAS ]

Reference： [1]Organic and Biomolecular Chemistry,2017,vol. 15,p. 9775 - 9778
[2]Organic Letters,2017,vol. 19,p. 1394 - 1397

29
[ 531-59-9 ]
[ 102061-82-5 ]
7-methoxy-3-(perfluorobutyl)-2H-chromen-2-one [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
68%	With tert.-butylhydroperoxide; copper diacetate; In dichloromethane; acetonitrile; at -5 - 20℃; for 25h;Inert atmosphere; Sealed tube;	General procedure: In a 5 mL Wheatton vial provided with a screw-cap septum and a micro stir bar, 0.2mmol of coumarin, 4 equiv. of Cu(OAc)2 and 3 equiv. of NaSO2C4F9 were mixed in3 mL of a 1:1 mixture of MeCN:CH2Cl2. The mixture was deoxygenated with a slow stream of Ar for 15 minutes, the vial closed and 5 equiv of tert-butylhydroperoxide,TBHP, were slowly added (1 hour) through the septum by microliter syringe while keeping the temperature at -5 C in an ice/salt bath. The cooled mixture was placed on a stir plate and stirred for 24 additional hours at room temperature. Brine was added to the crude reaction mixture and extracted into CH2Cl2 thrice. The organic layers were gathered and dried under anhydrous sodium sulfate, filtered,and evaporated under vacuo. The residue was chromatographed by preparative thin layer silica gel chromatography using a hexane:ethyl acetate as eluent or otherwise indicated in the characterization of each compound.

Reference： [1]Journal of Fluorine Chemistry,2017,vol. 197,p. 42 - 48

30
[ 74-83-9 ]
[ 93-35-6 ]
[ 531-59-9 ]

Yield	Reaction Conditions	Operation in experiment
86%	Stage #1: 7-hydroxy-2H-chromen-2-one With potassium carbonate In acetone for 0.25h; Inert atmosphere; Reflux; Stage #2: methyl bromide In acetone Inert atmosphere; Reflux;	General procedure for the synthesis of 7-O-alkylumbelliferone (1a-j): General procedure: In a 50 mL two necked round-bottomed flask equipped with a magnetic stirrer, a condenser, and a nitrogen inlet,umbelliferone (1 equiv.), K2CO3 (3 equiv.) and 10 mL of anhydrous acetone were added. The mixture was heated underreflux for 15 min under nitrogen atmosphere and cooledto room temperature before the dropwise addition of alkylbromide (1.5 equiv.). The resulting mixture was heated underreflux for another 2-6 h. The reaction was quenched withwater (10 mL), followed by extraction with EtOAc (2×50 mL)and washed with brine solution. After drying (Na2SO4) andremoval of the solvent, the residue was purified by columnchromatography using hexane/EtOAc as mobile phase (gradientelution), to afford the corresponding compounds 1aj14.All the derivatives were characterized by 1H, 13C NMRand mass data.
69.56%	Stage #1: 7-hydroxy-2H-chromen-2-one With potassium carbonate In acetone at 20℃; for 0.5h; Stage #2: methyl bromide In acetone at 65℃; for 24h;	15.6. Procedure for synthesis of coumarin derivatives A21-A25 General procedure: The synthetic route is shown in Scheme 2. For example, to a stirred solution of 7-hydroxycoumarin (0.16 g, 1 mmol) in 20 mL acetone were added anhydrous K2CO3 (0.28 g, 2 mmol) at room temperature. After stirring at room temperature for 30 min, bromopropane (0.21 g, 1.5 mmol) was added to the reaction mixture, and whole was refluxed at 65°C for 24 h. The precipitate was filtered off and washed with acetone (4 × 30 mL). The solvent was evaporated under reduced pressure, and the residue was treated with water (50 mL) and extracted with ethyl acetate (4 × 30 mL). The organic layer was combined, dried with anhydrous Na2SO4, and concentrated under reduced pressure. The obtained residue was purified by silica gel chromatography with mixed petroleum ether and ethyl acetate (3:1, v/v) as eluent to give compounds A21-A25 as solid. Compound A21. Yield 69.56%.1H NMR (500 MHz, CDCl3) δ 7.63 (d, J = 9.5 Hz, 1H), 7.36 (d, J = 8.6 Hz, 1H), 6.87 - 6.78 (m, 2H), 6.23 (d, J = 9.4 Hz, 1H), 3.86 (s, 3H). 13C NMR (126 MHz, CDCl3) δ 162.97, 161.29, 156.04, 143.52, 128.88, 113.22, 112.69, 112.66, 100.98, 55.89. ESI-MS m/z: 199.0382 ([M+Na]+).
	With potassium carbonate In acetone at 80℃; for 1h;

In acetone at 80℃; for 1h;

Reference： [1]Yadav, Nisha; Auti, Prashant; George, Ginson; Paul, Atish T. [Journal of the Indian Chemical Society, 2020, vol. 97, # 8, p. 1265 - 1271]
[2]Chen, Jiong; Hu, Yang; Liu, Lei; Qiu, Tianxiu; Shan, Lipeng [European Journal of Medicinal Chemistry, 2021, vol. 223]
[3]Gargaro, Marco; Epifano, Francesco; Fiorito, Serena; Taddeo, Vito Alessandro; Genovese, Salvatore; Pirro, Matteo; Turco, Antonella; Puccetti, Paolo; Schmidt-Weber, Carsten B.; Fallarino, Francesca [Journal of Natural Products, 2017, vol. 80, # 6, p. 1939 - 1943]
[4]Genovese, Salvatore; Epifano, Francesco; Medina, Philippe de; Caron, Nicolas; Rives, Arnaud; Poirot, Marc; Poirot, Sandrine Silvent; Fiorito, Serena [Bioorganic Chemistry, 2019, vol. 87, p. 181 - 190]

31
[ 614-45-9 ]
[ 531-59-9 ]
[ 24318-41-0 ]

Yield	Reaction Conditions	Operation in experiment
84%	With copper diacetate; at 100℃; for 24h;Schlenk technique; Inert atmosphere; Sealed tube;	A 10-ml Schlenk tube was charged with Cu(OAc)2 (18 mg, 5 mol%) and coumarin 10(0.41 g, 2 mmol). The tube was evacuated and backfilled with nitrogen thrice. TBPB (0.78 g,4 mmol) in methylanisole (10 ml) was added by syringe. The tube was then sealed, andthe mixture was stirred at 100 C for 24 h. Upon completion of the reaction, the mixturewas diluted with EtOAc. The solvent was then removed under vacuum. The residue waspurified by chromatography on silica gel (gradient eluent of EtOAc/petroleum ether, 1:30)to give compound 11 (0.81 g), as a colourless liquid (yield 84% based on TBPB). 1H NMR(400 MHz, CDCl3) delta: 8.07-8.04 (m, 2H), 7.53-7.50 (m, 1H), 7.43-7.38 (m, 4H), 6.94-6.89(m, 2H), 5.29 (s, 2H), 3.80 (s, 3H); 13C NMR (100 MHz, CDCl3) delta: 166.5, 159.7, 133.0,130.3, 130.1, 129.7, 128.4, 128.2, 114.0, 66.6, 55.3; ESI-MS: m/z 243.3 [M + H]+, which wasidentical to that in the literature

Reference： [1]Journal of Asian Natural Products Research,2017,vol. 19,p. 903 - 909

32
[ 673-22-3 ]
[ 108-24-7 ]
[ 531-59-9 ]

Yield	Reaction Conditions	Operation in experiment
78%	With sodium acetate; In N,N-dimethyl-formamide; at 180℃; for 6h;Inert atmosphere;	Under nitrogen atmosphere, a mixture of 2-hydroxy-4-methoxybenzaldehyde 9 (2.6 g,17.1 mmol), NaOAc (4.2 g, 51.3 mmol), and ethanoyl ethanoate (7.15 g, 70 mmol) in DMF30 ml was stirred at 180 C for 6 h. After the reaction mixture was cooled, it was addedto 100 ml 10% HCl, then extracted with EtOAc (30 ml × 3). The combined organic phasewas washed with brine, dried over Na2SO4, and concentrated under reduced pressure. Theresidue was recrystallized from water-alcohol to give the product 10 (2.35 g, 78% yield) asa white solid, m.p. 141-143 C, 1H NMR (400 MHz, CDCl3) delta: 7.65 (d, J = 9.5 Hz, 1H), 7.38(d, J = 8.6 Hz, 1H), 6.84 (dd, J = 8.6, 2.4 Hz, 1H), 6.80 (d, J = 2.4 Hz, 1H), 6.24 (d, J = 9.5 Hz,1H), 3.87 (s, 3H); 13C NMR (100 MHz, CDCl3) delta: 162.8, 161.2, 155.8, 143.4, 128.8, 113.0,112.5, 112.5, 100.8, 55.7.

Reference： [1]Journal of Asian Natural Products Research,2017,vol. 19,p. 903 - 909
[2]Organic Letters,2019,vol. 21,p. 2064 - 2068
[3]Journal of Organic Chemistry,2020,vol. 85,p. 7674 - 7682
[4]Synlett,2019,vol. 30,p. 1585 - 1591

33
[ 531-59-9 ]
[ 68-12-2 ]
[ 108734-15-2 ]

Yield	Reaction Conditions	Operation in experiment
70.12%		0.876 g (4.97 mmol) of <strong>[531-59-9]7-methoxycoumarin</strong> was dissolved in 2 mL (26.03 mmol) of DMF,Ice salt bath,When the temperature is maintained at -5 C,A mixture of 1.39 g (4.7 mmol) of BTC and 5 mL of trichloromethane was slowly added dropwise,Control finished in 30min.DMF all drip after the use of oil bath,Heating, control temperature 70 ,The reaction was monitored by TLC and the reaction was carried out for 6 h80 mL of water in the ice salt bath for 10min,With 10mLDCM extraction, combined with organic phase vacuum distillation,Ethanol to give 0.72 g of 3-formyl-<strong>[531-59-9]7-methoxycoumarin</strong> solid,Yield 70.12%.Melting point 235.8 ~ 237.5 .

Reference： [1]Patent: CN106957291,2017,A .Location in patent: Paragraph 0024-0026

34
[ 531-59-9 ]
C₁₀H₁₀N₂O₂ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
70%		<strong>[531-59-9]7-Methoxycoumarin</strong> (500 mg) and Lawson Reagent (1.86 g) were refluxed in dry toluene for 6 hours. After the reaction, cooling filter, the filtrate was dried and dissolved in ethanol, add 80% hydrazine hydrate, the reaction was refluxed for 3 hours. After completion of the reaction, the solvent was dried, water was added and extracted with dichloromethane. The organic phases were combined, dried over anhydrous sodium sulfate and purified by column chromatography to give II-1 (yield 70%).

Reference： [1]Patent: CN106632188,2017,A .Location in patent: Paragraph 0029-0030

35
[ 531-59-9 ]
[ 51838-01-8 ]
5-amino-3-isobutyl-8-methoxy-1H-chromeno[3,4-c]pyridine-2,4(3H,10bH)-dione [ No CAS ]