Name: 613-54-7|2-Bromo-2'-acetonaphthone|95%
Brand: Ambeed
SKU: A576224
Rating: 94 (28 reviews)

1
[ 612-57-7 ]
[ 613-54-7 ]
[ 6634-83-9 ]

Reference： [1]Journal of the American Chemical Society,1951,vol. 73,p. 3499

2
[ 17356-08-0 ]
[ 613-54-7 ]
[ 21331-43-1 ]

Yield	Reaction Conditions	Operation in experiment
96%	at 20℃;	4.2 General procedure for the synthesis of 2-(3-pyridyl)/2-amino thiazole derivatives (3/5) General procedure: A mixture of phenacyl bromide (1a) (10.0mmol), pyridine-3-carbothioamide/thiourea (2/4) (10.0mmol) and 5.0wt% of silica-supported HClO4 was taken in a mortar and ground together with a pestle for 5-10min at RT. At this stage, the progress of the reaction was monitored by TLC. After completion of the reaction, the crude mass was washed with water (20mL) twice and extracted with ethyl acetate (10mL) twice. Then the catalyst was separated by filtration under vacuum. The organic layer was washed with water, dried with anhydrous Na2SO4 and the solvent was evaporated under reduced pressure. The obtained product (3a/5a) was purified by recrystallization using ethanol. The same procedure was applied for the preparation of all other compounds (3b-k & 5b-k). All the compounds gave satisfactory physical and spectroscopic data following their proposed procedure. Compounds 5a-d and 5f-5k were synthesized and reported in the literature [82,83].
94%	In water monomer at 20℃; for 1h;
79%	In ethanol for 2h; Reflux;

40%	In ethanol at 50℃; for 0.5h; Microwave irradiation;
	In ethanol
	Stage #1: thiourea; 2-Bromo-2'-acetonaphthone In water monomer; ethyl acetate at 35 - 40℃; for 0.833333h; Stage #2: With sodium hydroxide In water monomer at 25 - 30℃; for 2h;	3.2 Ethyl acetate (120ml) was stirred at room temperature and 2- acetonaphthone (20.49g, 0.12mol) was added followed by tetrabutylammonium bromide (7.7g 0.024mol). Bromine (6.8ml 21.1g, 0.132mol) was then added dropwise, over 1 hour, at 30-350C. The mixture was stirred at 30 to 40° C for 30min. Water (90ml) was then added dropwise over 5 min. The temperature was raised to 350C and thiourea (8.2g. 0.11 mol) added portion-wise over 10 min. The reaction mixture was then stirred for 30 min at 35 to 4O0C. The white precipitate which formed was filtered, washed with ethyl acetate (60ml) then distilled water (30ml) to give 50.57g of a wet solid.The above solid was then added to a solution of sodium hydroxide (12.9g. 0.32mol) in water (240ml) and stirred at 25-3O0C for 2 hour. The resultant beige solid was filtered, washed with water then isopropanol and dried at 6O0C. The yield was19.29g (71 %)
	In ethanol for 2h; Reflux;	5.1.2. General procedure for the synthesis of 4-(2-chlorophenyl)thiazol-2-amine General procedure: The crude 2-bromo-1-(2-chlorophenyl)ethanone (0.64 mL, 4.28 mmol) was dissolved in anhydrous ethanol (10 mL) and treated with thiourea (344 mg, 4.51 mmol). After heating at reflux for 2 h, the reaction mixture was cooled to room temperature, with a yellow precipitation. The solid obtained was filtered, washed with water and ethanol and vacuum dried to afford 4b as a yellow solid (884 mg, 98.0%).
	With potassium carbonate In ethyl acetate for 5h; Reflux;
	at 20℃; for 4h; Ionic liquid;
5.4 g	In water monomer at 95℃; for 2h;	6.2 Synthesis of Intermediate (d-6) 22.5 g of the wet cake of Intermediate (c-6) was suspended in 110 mL of water, and 5.7 g of thiourea wasadded. After stirring at the internal temperature of 95°C for 2 hours, cooling was performed to room temperature. Afterthe reaction solution was neutralized by 25% ammonia water, the crystal was separated by filtration, and washed with50 mL of water. The crystal was suspended in 10 mL of methanol and 10 mL of ethanol, and stirred under reflux for 30minutes. After cooling to the internal temperature of 15°C, the crystal was separated by filtration to obtain 5.4 g of awhite crystal of Intermediate (d-6).
	In ethanol at 20℃; Reflux;	General procedure of 2-aminothiazole derivatives 2a-h General procedure: 2-Bromo-1-arylethanones (0.015 mol) were added to a solution of thiourea (1.5 g, 0.02 mol) in ethanol (50 mL).The mixture was reflux for 8 h and then cooled down to room temperature. The solvent was removed to half its volume in vacuum. The residue was brought to about pH 9 using ammonia. The mixture was extracted by EtOAc, and the extract was washed with saturated NaCl solution and dried over anhydrous Na2SO4. The solvent was removed in vacuum to give a precipitate which was crystallized from ethanol to afford the target compounds 2a-h.
	With copper (II) bromide In ethanol for 2h; Reflux;
	Reflux;
	In ethanol at 20℃; for 1h;	General synthesis of 4-(substituted aryl)thiazol-2-amine (1, 2, 3) 2-bromo-1-(naphthalen-2-yl)ethan-1-one (3.0 g, 12.043mmol)was reacted with thiourea (0.917 g, 12.043mmol) in ethanol(20mL) for 1 h at room temperature to obtain 4-(naphthalen-2-yl)-1,3-thiazol-2-amine (1). Likewise, with the same reactionconditions, 2-bromo-1-(4-chlorophenyl)ethan-1-one (3.0 g,13.096mmol) was reacted with thiourea (0.997 g, 13.096mmol)to obtain 4-(4-chlorophenyl)-1,3-thiazol-2-amine (2); and 2-bromo-1-(4-methoxyphenyl)ethan-1-one (3 g, 13.096mmol)with thiourea (0.997 g, 13.096mmol) to obtain 4-(4-methoxyphenyl)-1,3-thiazol-2-amine (3). The reaction was monitoredusing TLC. The mixture was filtered after the reaction was finished,and the residue was recrystallized using ethanol.
	With triethylamine In ethanol at 20℃; for 3h; Reflux;	General procedure of synthesis of 2-aminothiazolederivatives 3-6 General procedure: The mixture of phenacyl bromide derivatives 1 (0.1 mol) and thiourea 2 (0.11 mol) in anhydrous ethanol (100 ml) was heated at reflux for 3 h in presence of drops of trimethylamine (TEA). After that, the solvent was removed and a saturated aqueous NaHCO3 was added to adjust the pH to about 8-9. Then, the mixture was filtered to afford 3-6 as a white solids.
	With triethylamine In ethanol at 20℃; for 3h; Reflux;	General procedure of synthesis of 2-aminothiazolederivatives 3-6 General procedure: The mixture of phenacyl bromide derivatives 1 (0.1 mol) and thiourea 2 (0.11 mol) in anhydrous ethanol (100 ml) was heated at reflux for 3 h in presence of drops of trimethylamine (TEA). After that, the solvent was removed and a saturated aqueous NaHCO3 was added to adjust the pH to about 8-9. Then, the mixture was filtered to afford 3-6 as a white solids.

Reference： [1]Chellappa Subramanyam, Dwaraka Viswanath; Divi, Haranath; Godugu, Kumar; Gundala, Trivikram Reddy; Loka, Subramanyam Sarma; Mohinuddin Pinjari, Mohammad Khaja; Reddy Nallagondu, Chinna Gangi; Shaik, Sultana; Vemula, Venkatramu [Dyes and Pigments, 2021, vol. 187]
[2]Potewar, Taterao M.; Ingale, Sachin A.; Srinivasan, Kumar V. [Tetrahedron, 2008, vol. 64, # 22, p. 5019 - 5022]
[3]Dai, Weiyang; Samanta, Soma; Xue, Ding; Petrunak, Elyse M.; Stuckey, Jeanne A.; Han, Yanyan; Sun, Duxin; Wu, Yong; Neamati, Nouri [Journal of Medicinal Chemistry, 2019, vol. 62, # 6, p. 3068 - 3087]
[4]Annadurai, Sivakumar; Martinez, Rogelio; Canney, Daniel J.; Eidem, Tess; Dunman, Paul M.; Abou-Gharbia, Magid [Bioorganic and Medicinal Chemistry Letters, 2012, vol. 22, # 24, p. 7719 - 7725]
[5]Skowronska [Roczniki Chemii, 1949, vol. 23, p. 313,317][Chem.Abstr., 1951, p. 5682]
[6]Apparao,M. et al. [Journal of the Indian Chemical Society, 1975, vol. 52, p. 168]
[7]Current Patent Assignee: FUJIFILM HOLDINGS CORP. - WO2009/101428, 2009, A1 Location in patent: Page/Page column 31
[8]Location in patent: experimental part Xu, Qinyuan; Huang, Li; Liu, Juan; Ma, Liang; Chen, Tao; Chen, Jinying; Peng, Fei; Cao, Dong; Yang, Zhuang; Qiu, Neng; Qiu, Jingxiang; Wang, Guangcheng; Liang, Xiaolin; Peng, Aihua; Xiang, Mingli; Wei, Yuquan; Chen, Lijuan [European Journal of Medicinal Chemistry, 2012, vol. 52, p. 70 - 81]
[9]Location in patent: experimental part Yin, Guodong; Ma, Junrui; Shi, Houqiang; Tao, Qing [Heterocycles, 2012, vol. 85, # 8, p. 1941 - 1948]
[10]Muthyala, Manoj Kumar; Kumar, Anil [Journal of Heterocyclic Chemistry, 2012, vol. 49, # 4, p. 959 - 964]
[11]Current Patent Assignee: FUJIFILM HOLDINGS CORP. - EP2604656, 2013, A1 Location in patent: Paragraph 0337; 0339
[12]Ghabbour, Hazem A.; Kadi, Adnan A.; Eltahir, Kamal E. H.; Angawi, Rihab F.; El-Subbagh, Hussein I. [Medicinal Chemistry Research, 2015, vol. 24, # 8, p. 3194 - 3211]
[13]Ma, Liang; Wang, Taijin; Shi, Min; Ye, Haoyu [Drug Design, Development and Therapy, 2016, vol. 10, p. 1807 - 1815]
[14]Gundala, Trivikram Reddy; Godugu, Kumar; Nallagondu, Chinna Gangi Reddy [Journal of the Chinese Chemical Society, 2017, vol. 64, # 12, p. 1408 - 1416]
[15]Dawbaa, Sam; Evren, Asaf Evrim; Cantürk, Zerrin; Yurttaş, Leyla [Phosphorus, Sulfur and Silicon and the Related Elements, 2021, vol. 196, # 12, p. 1093 - 1102]
[16]Aboelenin, Mohamad M.; Mahrous, Karima F.; Othman, Abdelmageed M.; Sroor, Farid M. [Medicinal Chemistry Research, 2022, vol. 31, # 3, p. 400 - 415]
[17]Aboelenin, Mohamad M.; Mahrous, Karima F.; Othman, Abdelmageed M.; Sroor, Farid M. [Medicinal Chemistry Research, 2022, vol. 31, # 3, p. 400 - 415]

3
[ 613-54-7 ]
[ 55117-00-5 ]

Yield	Reaction Conditions	Operation in experiment
100%	With sodium azide In dimethyl sulfoxide at 10 - 20℃; for 1.5h; Inert atmosphere;	4.4. General method for synthesis of a-azido aryl ketones,illustrated for the preparation of 2-azido-1-(2-naphthyl)-ethanone 16a General procedure: 4.4. General method for synthesis of a-azido aryl ketones,illustrated for the preparation of 2-azido-1-(2-naphthyl)-ethanone 16a 2-(Bromoacetyl)naphthalene (2.00 g, 8.03 mmol) was dissolvedin DMSO (10 mL) and the mixture was cooled on ice such that thetemperature was kept below 10 C. Sodium azide (0.630 g,9.64 mmol) was added in one portion and the reaction was stirredunder argon at room temperature for 90 min. The reaction wasquenched with H2O (20 mL), and extracted with EtOAc(3 30 mL). The organic layers were combined, washed withH2O, dried (Na2SO4) and filtered. The solvent was removed invacuo to give the title compound as a brown/orange oil (1.69 g,8.01 mmol, 100%) with NMR consistent with literature values.43
96%	With sodium azide
96%	With sodium azide In tetrahydrofuran; acetonitrile at 20℃; for 2h;

94%	With sodium azide In dimethyl sulfoxide at 0 - 23℃; Inert atmosphere;
90.3%	With sodium azide In dimethyl sulfoxide at 20℃; for 1.5h; Inert atmosphere;	1.1 Step 12-azido-1 -(2-naphthyl)ethanon2-(bromoacetyl)naphthalene (2.00 g, 8.03 mmol) was dissolved in DMSO (10 mL) and the mixture was cooled on ice such that the temperature was kept below 10°C. Sodium azide (0.630 g, 9.64 mmol) was added in one portion and the reaction was stirred under argon at RT for 90 min. The reaction was quenched with H20 (20 mL), and extracted with EtOAc (3 x 30 mL). The organic layers were combined, washed with H20, dried (Na2S04) and filtered. The solvent was removed in vacuo to give brown/orange oil (1.53 g, 7.25 mmol, 90.3 %) with NMR consistent with literature values. Rf = 0.63 (5:1 Pet Ether/ EtOAc); IR (vmax/cm"1, thin film): 2105 (-N=N+=N" Stretch), 1690 (C=0 Stretch); 1 H NMR (600 MHz, CDCI3): δΗ = 4.73 (s, 2H, 1-H), 7.61 (t, J = 7.6 Hz, 1 H, 7-H), 7.66 (t, J = 7.6 Hz, 1 H, 8-H), 7.91 (d, J = 8.1 Hz, 1 H, 9-H), 7.95(d, J = 8.6 Hz, 1 H, 1 1-H), 7.99(m 2H, 6,12-H), 8.42 (s, 1 H, 4-H); 13C NMR (150 MHz, CDCI3): 5c = 55.0 (C-1 ), 123.3 (C-12), 127.2 (C-7), 127.9 (C-9) 129.0 (C-1 1 ), 129.1 (C-8), 129.6 (C-6), 129.8 (C-4), 131.7, 132.4 (C-5,10), 136.0 (C-3), 193.2 (C-2); LRMS m/z (ΕΓ): 21 1 [M]+, 155 [M-CH2N3]+, 127 [Naphthalene]".
73%	With sodium azide In glycerol at 25℃; for 3h;
71%	With sodium azide In acetone at 20℃; for 1h;
	With sodium azide; ethanol; acetic acid
	With sodium azide In water; acetone at 20℃; for 1h;
	With sodium azide In dimethyl sulfoxide at 10 - 20℃;
	With sodium azide In acetone at 20℃; for 24h;	137.1 To 2-bromo-1-(2-naphthyl)ethanone in acetone was added NaN3 (1 eq.) and the mixture was stirred at RT for 24 h. EtOAc was added (10 vol.) and the mixture was filtered. The filtrate was concentrated under reduced pressure and the residue was purified by flash chromatography on silica eluting with 10% EtOAc/Petroleum ether to obtain the product as a white solid.
	With sodium azide In water; acetone at 20℃; for 1h;
	With sodium azide In ethanol; water at 20℃;
	With sodium azide In dimethyl sulfoxide at 20℃; for 0.166667h;
	With sodium azide; acetic acid In ethanol; water Cooling;
	With sodium azide In N,N-dimethyl-formamide at 60℃; for 6h;
	With sodium azide In water; acetone at 0 - 20℃;
	With sodium azide
	With sodium azide In water; acetone
	With sodium azide

Reference： [1]Sayer, James R.; Walldn, Karin; Pesnot, Thomas; Campbell, Frederick; Gane, Paul J.; Simone, Michela; Koss, Hans; Buelens, Floris; Boyle, Timothy P.; Selwood, David L.; Waksman, Gabriel; Tabor, Alethea B. [Bioorganic and Medicinal Chemistry, 2014, vol. 22, # 22, p. 6459 - 6470]
[2]Prasad, Budaganaboyina; Phanindrudu, Mandalaparthi; Tiwari, Dharmendra Kumar; Kamal, Ahmed [Journal of Organic Chemistry, 2019, vol. 84, # 19, p. 12334 - 12343]
[3]Del Vecchio, Antonio; Talbot, Alex; Caillé, Fabien; Chevalier, Arnaud; Sallustrau, Antoine; Loreau, Olivier; Destro, Gianluca; Taran, Frédéric; Audisio, Davide [Chemical Communications, 2020, vol. 56, # 78, p. 11677 - 11680]
[4]Maulide, Nuno; Riomet, Margaux; Roller, Alexander; Zhang, Haoqi [Organic Letters, 2020]
[5]Current Patent Assignee: UNIVERSITY OF LONDON - WO2012/168733, 2012, A1 Location in patent: Page/Page column 36
[6]Vitale, Paola; Cicco, Luciana; Messa, Francesco; Perna, Filippo Maria; Salomone, Antonio; Capriati, Vito [European Journal of Organic Chemistry, 2019, vol. 2019, # 31-32, p. 5557 - 5562]
[7]Moumne, Roba; Larue, Valery; Seijo, Bili; Lecourt, Thomas; Micouin, Laurent; Tisne, Carine [Organic and Biomolecular Chemistry, 2010, vol. 8, # 5, p. 1154 - 1159]
[8]Boyer; Straw [Journal of the American Chemical Society, 1952, vol. 74, p. 4506]
[9]Chung, Florence; Tisne, Carine; Lecourt, Thomas; Dardel, Frederic; Micouin, Laurent [Angewandte Chemie - International Edition, 2007, vol. 46, # 24, p. 4489 - 4491]
[10]Shang, Gao; Liu, Duan; Allen, Scott E.; Yang, Qin; Zhang, Xumu [Chemistry - A European Journal, 2007, vol. 13, # 27, p. 7780 - 7784]
[11]Current Patent Assignee: MERCK & CO INC - US2009/48228, 2009, A1 Location in patent: Page/Page column 66
[12]Location in patent: experimental part Chung, Florence; Tisne, Carine; Lecourt, Thomas; Seijo, Bili; Dardel, Frederic; Micouin, Laurent [Chemistry - A European Journal, 2009, vol. 15, # 29, p. 7108 - 7116]
[13]Cuetos, Aníbal; Bisogno, Fabricio R.; Lavandera, Iván; Gotor, Vicente [Chemical Communications, 2013, vol. 49, # 26, p. 2625 - 2627]
[14]Kim, Yongjin; Pak, Han Kyu; Rhee, Young Ho; Park, Jaiwook [Chemical Communications, 2016, vol. 52, # 39, p. 6549 - 6552]
[15]Rodríguez-Hernández, Diego; Barbosa, Luiz C.A.; Demuner, Antonio J.; Nain-Perez, Amalyn; Ferreira, Sebastião R.; Fujiwara, Ricardo T.; de Almeida, Raquel M.; Heller, Lucie; Csuk, René [European Journal of Medicinal Chemistry, 2017, vol. 140, p. 624 - 635]
[16]Xu, Xiaoying; Zhang, Kaifan; Li, Panpan; Yao, Hequan; Lin, Aijun [Organic Letters, 2018, vol. 20, # 7, p. 1781 - 1784]
[17]Bangalore, Pavan K.; Vagolu, Siva K.; Bollikanda, Rakesh K.; Veeragoni, Dileep K.; Choudante, Pallavi C.; Misra, Sunil; Sriram, Dharmarajan; Sridhar, Balasubramanian; Kantevari, Srinivas [Journal of Natural Products, 2020, vol. 83, # 1, p. 26 - 35]
[18]Borra, Satheesh; Borkotoky, Lodsna; Newar, Uma Devi; Das, Babulal; Maurya, Ram Awatar [Advanced Synthesis and Catalysis, 2020, vol. 362, # 16, p. 3364 - 3368]
[19]Prasad, Budaganaboyina; Phanindrudu, Mandalaparthi; Nanubolu, Jagadeesh Babu; Kamal, Ahmed; Tiwari, Dharmendra Kumar [Chemical Communications, 2021, vol. 57, # 75, p. 9542 - 9545]
[20]Borkotoky, Lodsna; Borra, Satheesh; Maurya, Ram Awatar [European Journal of Organic Chemistry, 2022, vol. 2022, # 2]

4
[ 93-08-3 ]
[ 613-54-7 ]

Yield	Reaction Conditions	Operation in experiment
100%	With tetra-N-butylammonium tribromide In methanol; dichloromethane at 20℃; for 15h;	57.A Step A: A solution of tetrabutylammonium tribromide (15.6 g, 32 mmol) in dichloromethane (80 ml) was added dropwise to a solution of 2-acetylnaphthalene (5.0 g, 29 mmol) in dichloromethane (20 ml) and methanol (20 ml) at room temperature. At completion of the addition, the resulting red-orange solution was stirred at room temperature for 15 hours. The mixture was concentrated under vacuum and the residue was taken into ethyl acetate and water. The layers were separated and the aqueous phase was extracted with ethyl acetate. The combined organic extracts were washed with saturated aqueous sodium bicarbonate and brine and dried over anhydrous sodium sulfate to give the desired bromo compound (7.6 g, 100%): 1HNMR (300 MHz, CDCl3) δ 8.05 (s, 1H), 7.04 (dd, J=4.2, 1.8 Hz, 1 H), 8.02 (d, J=1.8 Hz, 1H), 7.56-7.67 (m, 2H), 4.59 (s, 2H).
97%	With potassium peroxomonosulfate; ammonium bromide In methanol for 0.333333h; Reflux; regioselective reaction;	2. General procedure General procedure: Oxone (1.352 g, 2.2 mmol) was added to the well stirred solution of substrate (2 mmol) and NH4Br (0.215 g, 2.2 mmol) in methanol (10 ml) and the reaction mixture was allowed to stir at room temperature (or reflux temperature). After completion of the reaction, as monitored by TLC, the reaction mixture was quenched with aqueous sodium thiosulfate, and extracted with ethyl acetate (3×25 ml). Finally, the combined organic layer was washed with water, dried over anhydrous sodium sulfate, filtered and removal of solvent in vacuo yielded a crude residue, which was further purified by column chromatography over silica gel (finer than 200 mesh) to afford pure products. All the products were identified on the basis of 1H NMR and mass spectral data.
97%	With copper (II) bromide In ethyl acetate for 3h; Reflux;

91%	With copper(II) bromide In ethanol at 60℃; Inert atmosphere;
91%	With NBS In methanol at 60 - 65℃; for 0.2h;
91%	With NBS; mesoporous silica In methanol for 0.316667h; Reflux;
88%	With NBS; silicium tetrachloride In acetonitrile at 20℃; for 6h;	Typical procedure for the halogenations of 1 or 6 with SiCl₄/NXS General procedure: To a mixture of NXS and substrate (1 or 6) in CH3CN at room temperature was added SiCl4 and the mixture left to stir until TLC showed the disappearance of the starting material. The reaction was then poured onto H2O and the mixture extracted with CH2Cl2. The extracts were combined, dried over MgSO4 and evaporated. The residue was purified by recrystallization (pet. ether-Et2O, 3:1) to give pure 2b-2g, 3b, or by silica gel column chromatography (hexane-EtOAc 10:1 or 30:1) to give pure 2a,h,i, 3a-5 or 7-9, respectively
87%	With NBS; ammonium acetate In diethyl ether at 25℃; for 0.5h;
86%	With hydrogen bromide; potassium iodide; NaNO₂ In lithium hydroxide monohydrate; acetonitrile at 0 - 20℃; for 10h;	General experimental procedure General procedure: In a RBF cooled in ice bath at 0 C, HBr(12 mmol, in 2 ml of water) was taken. To this a solution of NaNO2(5 mmol, in 5ml of water) was added drop wise. The reaction was stirred for 15min maintaining the temperature at 0 °C and KI (5 mol %) was added. After 10 min ketone(10 mmol) was added at once. After 15 min reaction temperature was brought to room temperature slowly. Reaction was monitored by TLC (ethyl acetate: pet ether, 1:9). After completion of reaction 50 ml of CHCl3 was added and organic layer separated. Aqueous layer was extracted with 25 ml of CHCl3 and combined organic layer was washed with 10% NaHSO3 solution (2 x 20 ml) and 10% NaHCO3 solution (2 x 20 ml).The organic layer was dried over sodium sulphate and concentrated under reduced pressure. Pure product was obtained after column chromatography (silica gel, 60-120, eluentethyl acetate: pet ether).
82%	With bromine In chloroform at 20℃; for 2.5h; Inert atmosphere;
82%	With carbon tetrabromide; tetra-n-butylammonium tetrafluoroborate In methanol; acetonitrile Inert atmosphere; Heating; Electrochemical reaction;
78%	With NBS; toluene-4-sulfonic acid In acetonitrile at 85℃; for 4h;	5.1-Aryl-2-bromoethanones (15a-i) General procedure: A mixture of substituted arylethanones 14a-i (10 mmol), N-bromosuccinimide (1.4 g, 12 mmol) and p-toluenesulphonic acid (2.8 g, 15 mmol) in acetonitrile (50 mL) was stirred at 85 °C for 4 h. After completion of reaction (indicated by TLC), the reaction mass was allowed to reach ambient temperature and evaporated excess of acetonitrile under reduced pressure. The residue so obtained was mixed in water, extracted with ethyl acetate (2 × 50 mL). The organic layer was dried over anhydrous Na2SO4 and concentrated in vacuuo. The crude product obtained was recrystallized from n-hexane to afford pure 1-aryl-2-bromoethanones 15a-i in 75-85% yields.
75%	With tetra-N-butylammonium tribromide In methanol; dichloromethane for 2h; Ambient temperature;
75%	With potassium bromate; lithium hydroxide monohydrate; potassium bromide In ethanol for 0.75h;
72%	With NBS; trimethylsilyl trifluoropmethanesulfonate In acetonitrile at 20℃; for 24h;
71%	With bromine In chloroform at 0 - 65℃;
50%	With copper (II) bromide In chloroform for 3h; Heating;
	With carbon disulfide; bromine
	With Carbon tetrachloride; bromine
	With bromine; glacial acetic acid
	With copper (II) bromide In chloroform; ethyl acetate for 3.5h; Heating;
	With bromine In Carbon tetrachloride
	With bromine Ambient temperature;
	With bromine
	With perchloric acid; bromine In lithium hydroxide monohydrate; glacial acetic acid at 30℃;
	With bromine; glacial acetic acid for 2h; Ambient temperature;
	With aluminium(III) chloride; bromine In diethyl ether
	With aluminium(III) chloride; bromine In diethyl ether at 0℃;
	With perchloric acid; bromine In lithium hydroxide monohydrate; glacial acetic acid at 30℃; further temperatures; ΔH(activ.), ΔS(activ.) and rate constants for enolisation step;
	With bromine In chloroform
	With hydrogenchloride; bromine In glacial acetic acid at 20℃;
	With bromine In glacial acetic acid
	With copper (II) bromide In chloroform; ethyl acetate Heating;
	With copper (II) bromide
	With aluminium(III) chloride; bromine In tetrahydrofuran at 0℃;
	With bromine In chloroform
	With bromine; glacial acetic acid at 20℃; for 6.5h;
	With tetrabutylammonium bromide; bromine In lithium hydroxide monohydrate; ethyl acetate at 20 - 40℃;	3.2 Ethyl acetate (120ml) was stirred at room temperature and 2- acetonaphthone (20.49g, 0.12mol) was added followed by tetrabutylammonium bromide (7.7g 0.024mol). Bromine (6.8ml 21.1g, 0.132mol) was then added dropwise, over 1 hour, at 30-350C. The mixture was stirred at 30 to 40° C for 30min. Water (90ml) was then added dropwise over 5 min. The temperature was raised to 350C and thiourea (8.2g. 0.11 mol) added portion-wise over 10 min. The reaction mixture was then stirred for 30 min at 35 to 4O0C. The white precipitate which formed was filtered, washed with ethyl acetate (60ml) then distilled water (30ml) to give 50.57g of a wet solid.The above solid was then added to a solution of sodium hydroxide (12.9g. 0.32mol) in water (240ml) and stirred at 25-3O0C for 2 hour. The resultant beige solid was filtered, washed with water then isopropanol and dried at 6O0C. The yield was19.29g (71 %)
	With bromine
	With copper (II) bromide In chloroform; ethyl acetate at 60℃;	3.5. Synthesis of the compound 7 series General procedure: To a solution of substituted methyl ketones (6, 20 mmol) in ethyl acetate (15 mL) and chloroform (15 mL), copper bromide (8.92 g, 40 mmol) was added in batches and it was slowly heated to 60 °C for 5-12 h, filtered while hot, the filtrate was washed with 10% hydrochloric acid (30 mL × 3) and water (30 mL × 3), dried with anhydrous sodium sulfate. After filtration the solvent was evaporated at reduced pressure and the compounds 7 were recrystallized from ethanol.
	With copper (II) bromide In ethanol; chloroform; ethyl acetate at 65℃; for 0.5h;	5.1.1. General procedure for the synthesis of 2-bromo-1-(2-chlorophenyl)ethanone General procedure: A solution of 1-(2-chlorophenyl)ethanone (2b) (0.84 mL, 6.5 mmol) in anhydrous ethyl acetate (25 mL) and chloroform (25 mL) was treated with copper (II) bromide (4.33 g, 19.5 mmol) and ethanol (6 mL), stirred at 65 °C for 0.5 h. The reaction was extracted with chloroform (40 mL). The organic extracts were washed with water (3 × 30 mL), dried (NaSO4), filtered, and concentrated in vacuo to give a colourless oil.
	With lithium hydroxide monohydrate; hydrogen bromide; bromine In chloroform at 0 - 20℃; for 4h;
	With copper(II) bromide In ethyl acetate Reflux;
	With Aluminum Chloride; bromine In methanol
	With trimethylphenylammonium perbromide at 20℃; for 2h; Ionic liquid;
	With bromine In glacial acetic acid
	With potassium peroxomonosulfate; ammonium bromide In methanol at 20℃; for 24h; Green chemistry; regioselective reaction;
	With NBS; toluene-4-sulfonic acid In acetonitrile for 1h; Reflux;	2.5 Synthesis of starting material 4 (4a as an example): General procedure: N-Bromobutanimide (NBS, 356 mg, 2.0 mmol) and 4-Methylbenzenesulfonic acid (PTSA, 344 mg, 2.0 mmol) were added to a well-stirred solution of aryl methyl ketone 8a (240 mg, 2.0 mmol) in anhydrous MeCN (15 mL). The mixture was stirred at room temperature for 1 h, and then refluxed for another 1-2.5 h. After disappearance of aryl methyl ketone 8a (monitored by TLC), the solvent was removed under reduced pressure, then added 50mL water to the mixture, extracted with EtOAc 3 times (3 × 50 mL). The extract was washed with 10% NaCl solution, dried over anhydrous Na2SO4 and concentrated under reduced pressure. The residue was puried by column chromatography on silica gel to yield the desired product 4a as a white solid in 90% yield.
	With bromine In ethyl acetate at 20℃; Inert atmosphere;
22.5 g	With bromine; glacial acetic acid at 15 - 20℃; for 1h;	6.1 Synthesis of Intermediate (c-6) A solution of 12.7 g of acetonaphthone and 50 mL of acetic acid was stirred at the internal temperature of 15°C,and 4.2 mL of bromine was added dropwise. The temperature was increased to room temperature, and stirring was thenperformed for 1 hour. The reaction mixture was added to 200 g of ice water and the crystal was separated by filtration.Washing was performed with 50 mL of water to obtain 22.5 g of a wet cake of Intermediate (c-6).
	With bromine In diethyl ether Inert atmosphere;
	With bromine In chloroform
	With pyridinium hydrobromide perbromide In ethanol; chloroform at 50℃; for 16h;	4.3. General method for synthesis of a-bromo aryl ketones,illustrated for the preparation of 2-bromo-1-(2-phenoxyphenyl)ethanone, 15b General procedure: 4.3. General method for synthesis of a-bromo aryl ketones,illustrated for the preparation of 2-bromo-1-(2-phenoxyphenyl)ethanone, 15b1-(2-Phenoxyphenyl)ethanone (2.00 g, 9.42 mmol) was dissolvedin chloroform (60 mL) and ethanol (60 mL). Pyridiniumtribromide (7.50 g, 23.6 mmol) was added and the reaction wasstirred at 50 C for 16 h. The reaction mixture was cooled to roomtemperature and the solvents removed in vacuo. The resultingorange slurry was suspended in H2O (30 mL) and extracted withEtOAc (4 30 mL). The combined organic extracts were washedwith H2O (2 20 mL) and brine (1 20 mL), dried (Na2SO4), filteredand concentrated in vacuo to give a yellow oil. Flashchromatography was carried out (applied in petroleum ether;eluted 0% to 10% to 33% CH2Cl2) to afford the title compound asa pale yellow oil (2.30 g, 7.90 mmol, 84%).
	With bromine
	With copper (II) bromide In chloroform; ethyl acetate at 65℃; for 0.5h;
	With bromine In diethyl ether
	With copper (II) bromide In chloroform; ethyl acetate for 2h; Reflux;
	With copper (II) bromide In chloroform; ethyl acetate at 90℃; for 3h;	100mL single-mouth flask, equipped with a reflux condenser, was added cupric bromide (8.934g, 40mmol), 2-acetylnaphthalene (3.404g, 20mmol). Add chloroform 10mL, ethyl acetate 10mL. Move to an oil bath at 90 deg.C and react for 3H; cooled to room temperature, the solid was filtered to give a liquid after spin dry column to give α-bromo-2-acetyl-naphthalene.
	With bromine In glacial acetic acid at 0 - 5℃;
4.6g	With bromine In chloroform at -10 - 20℃; for 1h;	27.A A) Preparation of 2-bromo-1-naphthalen-2-yl-ethanone To the stirred solution of 1-naphthalen-2-yl-ethanone (5.0 g, 29.0 mmol) in dry CHC13 (50 ml) was added bromine (1.5 mL, 29.0 mmol, in 15 ml CHC13) very slowly at -10 °C to 0 °C. After addition temperature of the reaction mixture was slowly raised to RT and stirred at RT for 1 h. The reaction was monitored by TLC and after completion of the reaction sodium thiosulphate solution was added to the reaction mixture and was subjected to a standard ethylacetate work up to give 1.0 g of the desired product as a liquid and was purified by column chromatography using 15 % ethyl acetate-hexane to give the pure desired product (4.6 g) as a liquid.
	With copper (II) bromide In ethanol at 60℃;
	With bromine In dichloromethane at 20℃;
	With NBS; citric acid In ethanol; lithium hydroxide monohydrate for 0.3h; Reflux;
	With NBS; toluene-4-sulfonic acid In acetonitrile at 50℃; for 24h;	Preparation of α-Amino Carbonyl Compounds General procedure: Synthesis of α-Aminocarbonyl Compounds by a Two-Step Method. First Step Synthesis of α-bromoacetophenone: to a solution of the acetophenone derivative (15.0 mmol, 1 equiv) in 8 mL of acetonitrile were added NBS (2.72 g, 15.3 mmol, 1.02 equiv) and p-toluenesulfonic acid (2.85 g, 15.0 mmol, 1 equiv). The reaction mixture was stirred for 24 h at 50 °C. After that time, the solvent was evaporated under reduced pressure. A water solution of saturated NaHCO3 (30 mL) was then added, and the solution was extracted with dichloromethane (3 × 30 mL). The organic layers were combined and dried over Na2SO4. The solvent was evaporated, and the residue was purified by silica gel column chromatography (petroleum ether/ethyl acetate = 25:1, V/V) to afford the desired product in 82% yield as a white solid. After that, α-bromoacetophenone (5 mmol) and with aniline (5 mmol) and NaHCO3 (5 mmol) were added to a stirred solution of EtOH (20 ml) at room temperature for 12 h. The crude product was filtered under reduced pressure to give a yellow precipitate, which was recrystallized by EtOH and the yellow solid was isolated in 86% yield.
	With bromine In diethyl ether at 0 - 20℃;
	With bromine In chloroform at 20℃; for 1h; Cooling with ice;	18.1 (1) Synthesis of 2-bromo-1-(naphthalen-2-yl)ethan-1-one Take 2-naphthylEthanone (1.7g, 10mmol) was dissolved in 100ml chloroform,Br2 (1.91 g, 12 mmol) was slowly added dropwise under ice bath, and the mixture was stirred at room temperature for 1 h.After the reaction, the reaction was quenched with saturated sodium sulfite and the organic layer was washed with saturated sodium hydrogen sulfate and brine.After dried over anhydrous sodium sulfate, the solvent was removed in vacuo to give a crude product 2.49g.
	With bromine; bromic acid; glacial acetic acid at 0 - 20℃;
	With copper(II) bromide In methanol for 1h; Reflux;
	With potassium peroxymonosulfate; ammonium bromide In methanol Reflux;
	With bromine In diethyl ether at 0 - 20℃;
	With copper (II) bromide In ethyl acetate Reflux;
	With NBS; toluene-4-sulfonic acid In acetonitrile at 90℃;
	With NBS; toluene-4-sulfonic acid In acetonitrile at 90℃; Inert atmosphere;	2.1 Synthesis of substituted bromoacetone General procedure: A mixture of N-bromosuccinimide (NBS, 2.94 g, 16.5 mmol, 1.1 equiv), p-toluenesulfonic acid(TsOH, 3.10 g, 18 mmol, 1.2 equiv) were added to substituted acyl (S1, 15 mmol, 1.0 equiv), then thereaction stirred at 90 oC for overnight. The reaction solvent was distilled off under reduced pressure,then neutralize the reaction with 5 mL of NaHCO3 saturated solution, dissolved in DCM (50 mL) andwashed with H2O (3×30 mL), dried over Na2SO4, then concentrated to give the substitutedbromoacetone (S2) as a white solid. The crude mixture S2 did not need to be purified and go to thenext reaction step directly
	With NBS; toluene-4-sulfonic acid In acetonitrile at 50℃; for 24h; Inert atmosphere;
	With α-bromination reagent
	Stage #1: methyl 2-naphthyl ketone With copper(II) bromide In ethyl acetate Inert atmosphere; Stage #2:
	With copper (II) bromide In ethyl acetate for 5h; Schlenk technique; Inert atmosphere; Reflux;
	With NBS; toluene-4-sulfonic acid at 0℃; for 4h; Inert atmosphere; Reflux;	General procedure: To the solution of bromosuccinimide (NBS, 1.2 equiv.) and p-Toluenesulfonic acid monohydrate (PTSA, 0.1 equiv.) in dichloromethane (DCM, 1 M) was added ketone (1.0 equiv.) at 0 °C, the reaction mixture was then brought to reflux over 4 hr. Upon completion of the reaction (TLC), the solution was treated with H2O and then extracted with DCM, washed with brine, and dried over anhydrous sodium sulfate. Removal of the solvent under vacuum afforded the crude product, which was purified by column chromatography on silica gel using hexane/ethyl acetate (EA) as eluent to afford the bromide (solvent ratio: 100/1 to 10/1)[1].
	Stage #1: methyl 2-naphthyl ketone With toluene-4-sulfonic acid In ethyl acetate for 0.166667h; Inert atmosphere; Stage #2: With NBS In ethyl acetate at 25℃; for 24h; Inert atmosphere;
	With NBS; toluene-4-sulfonic acid In ethyl acetate at 20℃; for 12h;
	With NBS; toluene-4-sulfonic acid In dichloromethane at 0℃; Reflux;
	With copper (II) bromide In ethyl acetate at 20℃;
	With copper (II) bromide In chloroform; ethyl acetate
	With NBS; toluene-4-sulfonic acid In acetonitrile at 25℃; Reflux;

Reference： [1]Current Patent Assignee: CURIA INC - US2006/52378, 2006, A1 Location in patent: Page/Page column 110
[2]MacHarla, Arun Kumar; Chozhiyath Nappunni, Rohitha; Marri, Mahender Reddy; Peraka, Swamy; Nama, Narender [Tetrahedron Letters, 2012, vol. 53, # 2, p. 191 - 195]
[3]Dai, Weiyang; Samanta, Soma; Xue, Ding; Petrunak, Elyse M.; Stuckey, Jeanne A.; Han, Yanyan; Sun, Duxin; Wu, Yong; Neamati, Nouri [Journal of Medicinal Chemistry, 2019, vol. 62, # 6, p. 3068 - 3087]
[4]Su, Qiong; Zhao, Zi-Jian; Xu, Feng; Lou, Peng-Cai; Zhang, Kai; Xie, De-Xun; Shi, Lei; Cai, Qing-Yun; Peng, Zhi-Hong; An, De-Lie [European Journal of Organic Chemistry, 2013, # 8, p. 1551 - 1557]
[5]Mohan, Reddy Bodireddy; Reddy, N. C. Gangi [Synthetic Communications, 2013, vol. 43, # 19, p. 2603 - 2614]
[6]Bodireddy, Mohan Reddy; Mahla, Ranjeet Singh; Khaja Mohinuddin, P. Md.; Reddy, G. Trivikram; Raghava Prasad, D. Vijaya; Kumar, Himanshu; Reddy, N. C. Gangi [RSC Advances, 2016, vol. 6, # 79, p. 75651 - 75663]
[7]Location in patent: experimental part Salama, Tarek A.; Novák, Zoltán [Tetrahedron Letters, 2011, vol. 52, # 31, p. 4026 - 4029]
[8]Location in patent: experimental part Wan, Jing; Zheng, Cai-Jun; Fung, Man-Keung; Liu, Xiao-Ke; Lee, Chun-Sing; Zhang, Xiao-Hong [Journal of Materials Chemistry, 2012, vol. 22, # 10, p. 4502 - 4510]
[9]Ghorpade, Archana K.; Huddar, Sameerana N.; Akamanchi, Krishnacharya G. [Tetrahedron Letters, 2016, vol. 57, # 44, p. 4918 - 4921]
[10]Location in patent: experimental part Kourounakis, Angeliki P.; Matralis, Alexios N.; Nikitakis, Anastasios [Bioorganic and Medicinal Chemistry, 2010, vol. 18, # 21, p. 7402 - 7412]
[11]Zhou, Zhilin; Yuan, Yong; Cao, Yangmin; Qiao, Jin; Yao, Anjin; Zhao, Jing; Zuo, Wanqing; Chen, Wenjie; Lei, Aiwen [Chinese Journal of Chemistry, 2019, vol. 37, # 6, p. 611 - 615]
[12]Venkataramana Reddy; Mishra, Shriprada; Tantak, Mukund P.; Nikhil, Kumar; Sadana, Rachna; Shah, Kavita; Kumar, Dalip [Bioorganic and Medicinal Chemistry Letters, 2017, vol. 27, # 6, p. 1379 - 1384]
[13]Kajigaeshi, Shoji; Kakinami, Takaaki; Okamoto, Tsuyoshi; Fujisaki, Shizuo [Bulletin of the Chemical Society of Japan, 1987, vol. 60, # 3, p. 1159 - 1160]
[14]Location in patent: experimental part Thirunarayanan; Vanangamudi; Sathiyendran; Ravi [Indian Journal of Chemistry - Section B Organic and Medicinal Chemistry, 2011, vol. 50, # 4, p. 593 - 604]
[15]Wang, Chao; Li, Zhilong; Ju, Yeming; Koo, Sangho [European Journal of Organic Chemistry, 2012, # 35, p. 6976 - 6985]
[16]Maji, Tapan; Karmakar, Ananta; Reiser, Oliver [Journal of Organic Chemistry, 2011, vol. 76, # 2, p. 736 - 739]
[17]Tomoda, Haruhiko; Hirano, Takafumi; Saito, Shojiro; Mutai, Toshiki; Araki, Koji [Bulletin of the Chemical Society of Japan, 1999, vol. 72, # 6, p. 1327 - 1334]
[18]Willemart [Annales de Chimie (Cachan, France), 1929, vol. <10> 12, p. 363][Comptes Rendus Hebdomadaires des Seances de l'Academie des Sciences, 1929, vol. 188, p. 1173] Rabcewicz-Zubkowski [Roczniki Chemii, vol. 9, p. 538][Chemisches Zentralblatt, 1929, vol. 100, # II, p. 2775]
[19]Weidlich; Daniels [Chemische Berichte, 1939, vol. 72, p. 1590,1595] Radcliffe; Sherwood; Short [Journal of the Chemical Society, 1931, p. 2293,2295]
[20]Immediata; Day [Journal of Organic Chemistry, 1940, vol. 5, p. 512,522] Kroehnke [Chemische Berichte, 1936, vol. 69, p. 921,924]
[21]Robertson; Krushinski; Beedle; Leander; Wong; Rathbun [Journal of Medicinal Chemistry, 1986, vol. 29, # 9, p. 1577 - 1586]
[22]Bedford; Miura; Bottaro; Howd; Nolen III [Journal of Medicinal Chemistry, 1986, vol. 29, # 9, p. 1689 - 1696]
[23]Lhotak, Pavel; Kurfuerst, Antonin [Collection of Czechoslovak Chemical Communications, 1993, vol. 58, # 8, p. 1898 - 1904]
[24]Bennett; Mullen; Allen; Mitchell; St. Georgiev [Arzneimittel-Forschung/Drug Research, 1989, vol. 39, # 10, p. 1206 - 1208]
[25]Rajasekaran, K.; Baskaran, T.; Gnanasekaran, C. [Indian Journal of Chemistry, Section A: Inorganic, Physical, Theoretical and Analytical, 1984, vol. 23, # 12, p. 1008 - 1010]
[26]Wahbi, Y.; Caujolle, R.; Tournaire, C.; Payard, M.; Linas, M. D.; Seguela, J. P. [European Journal of Medicinal Chemistry, 1995, vol. 30, # 12, p. 955 - 962]
[27]Barlin, Gordon B.; Davies, Les P.; Ireland, Stephen J. [Australian Journal of Chemistry, 1996, vol. 49, # 4, p. 443 - 449]
[28]Barlin, Gordon B.; Davies, Les P.; Harrison, Peter W.; Ireland, Stephen J.; Willis, Anthony C. [Australian Journal of Chemistry, 1996, vol. 49, # 4, p. 451 - 461]
[29]Rajasekaran, K.; Baskaran, T.; Gnanasekaran, C. [Indian Journal of Chemistry, Section A: Inorganic, Physical, Theoretical and Analytical, 1984, vol. 23, # 12, p. 1008 - 1010]
[30]Nam, Nguyen-Hai; Kim, Yong; You, Young-Jae; Hong, Dong-Ho; Kim, Hwan-Mook; Ahn, Byung-Zun [Bioorganic and Medicinal Chemistry Letters, 2001, vol. 11, # 23, p. 3073 - 3076]
[31]Kim, Yong; Nam, Nguyen-Hai; You, Young-Jae; Ahn, Byung-Zun [Bioorganic and Medicinal Chemistry Letters, 2002, vol. 12, # 4, p. 719 - 722]
[32]Arabaci, Gulnur; Yi, Tian; Fu, Hua; Porter, Mary E.; Beebe, Kirk D.; Pei, Dehua [Bioorganic and Medicinal Chemistry Letters, 2002, vol. 12, # 21, p. 3047 - 3050]
[33]Fitzgerald, Deirdre H.; Muirhead, Karen M.; Botting, Nigel P. [Bioorganic and Medicinal Chemistry, 2001, vol. 9, # 4, p. 983 - 989]
[34]Lv, Jian; Qian, Yunbo; Liu, Tingting; Wang, Yongmei [Bioorganic and Medicinal Chemistry Letters, 2007, vol. 17, # 15, p. 4102 - 4106]
[35]Khade, Prashant K.; Singh, Anil K. [Tetrahedron Letters, 2007, vol. 48, # 39, p. 6920 - 6923]
[36]Dang, Yizhe; Chen, Yi [Journal of Organic Chemistry, 2007, vol. 72, # 18, p. 6901 - 6904] Dang, Yizhe; Chen, Yi [European Journal of Organic Chemistry, 2007, # 34, p. 5661 - 5664]
[37]Location in patent: body text Kosmalski, Tomasz; Wojtczak, Andrzej; Zaidlewicz, Marek [Tetrahedron Asymmetry, 2009, vol. 20, # 10, p. 1138 - 1143]
[38]Location in patent: experimental part Zhan, Peng; Liu, Xinyong; Fang, Zengjun; Li, Zhenyu; Pannecouque, Christophe; De Clercq, Erik [European Journal of Medicinal Chemistry, 2009, vol. 44, # 11, p. 4648 - 4653]
[39]Current Patent Assignee: FUJIFILM HOLDINGS CORP. - WO2009/101428, 2009, A1 Location in patent: Page/Page column 31
[40]Location in patent: scheme or table Karakurt, Arzu; Özalp, Meral; Işik, Şamil; Stables, James P.; Dalkara, Sevim [Bioorganic and Medicinal Chemistry, 2010, vol. 18, # 8, p. 2902 - 2911]
[41]Location in patent: experimental part Li, Ting; Liu, Guyue; Li, Hongcai; Yang, Xinmei; Jing, Yongkui; Zhao, Guisen [Bioorganic and Medicinal Chemistry, 2012, vol. 20, # 7, p. 2316 - 2322]
[42]Location in patent: experimental part Xu, Qinyuan; Huang, Li; Liu, Juan; Ma, Liang; Chen, Tao; Chen, Jinying; Peng, Fei; Cao, Dong; Yang, Zhuang; Qiu, Neng; Qiu, Jingxiang; Wang, Guangcheng; Liang, Xiaolin; Peng, Aihua; Xiang, Mingli; Wei, Yuquan; Chen, Lijuan [European Journal of Medicinal Chemistry, 2012, vol. 52, p. 70 - 81]
[43]Location in patent: experimental part Zhu, Xiaohe; Li, Weipeng; Yan, Hong; Zhong, Rugang [Journal of Photochemistry and Photobiology A: Chemistry, 2012, vol. 241, p. 13 - 20]
[44]Location in patent: experimental part Yin, Guodong; Ma, Junrui; Shi, Houqiang; Tao, Qing [Heterocycles, 2012, vol. 85, # 8, p. 1941 - 1948]
[45]Location in patent: scheme or table Paul, Nidhin; Kaladevi, Selvam; Beneto, Arockiam Jesin; Muthusubramanian, Shanmugam; Bhuvanesh, Nattamai [Tetrahedron, 2012, vol. 68, # 34, p. 6892 - 6901]
[46]Muthyala, Manoj Kumar; Kumar, Anil [Journal of Heterocyclic Chemistry, 2012, vol. 49, # 4, p. 959 - 964]
[47]Karakurt, Arzu; Alagöz, Mehmet A.; Sayoǧlu, Burcu; Çalş, Ünsal; Dalkara, Sevim [European Journal of Medicinal Chemistry, 2012, vol. 57, p. 275 - 282]
[48]Naresh, Mameda; Arun Kumar, Macharla; Mahender Reddy, Marri; Swamy, Peraka; Nanubolu, Jagadeesh Babu; Narender, Nama [Synthesis, 2013, vol. 45, # 11, p. 1497 - 1504]
[49]Zhu, Yan-Ping; Cai, Qun; Gao, Qing-He; Jia, Feng-Cheng; Liu, Mei-Cai; Gao, Meng; Wu, An-Xin [Tetrahedron, 2013, vol. 69, # 31, p. 6392 - 6398]
[50]Liu, Xiang-Wei; Wang, Chao; Yan, Yan; Wang, Yong-Qiang; Sun, Jian [Journal of Organic Chemistry, 2013, vol. 78, # 12, p. 6276 - 6280]
[51]Current Patent Assignee: FUJIFILM HOLDINGS CORP. - EP2604656, 2013, A1 Location in patent: Paragraph 0337; 0338
[52]Chen, Jianzhong; Liu, Delong; Butt, Nicholas; Li, Chao; Fan, Dongyang; Liu, Yangang; Zhang, Wanbin [Angewandte Chemie - International Edition, 2013, vol. 52, # 44, p. 11632 - 11636][Angew. Chem., 2013, vol. 125, # 44, p. 11846 - 11850,5]
[53]Qu, Li; Makarov, Nikolay S.; Zhong, Cheng; Perry, Joseph W.; Qin, Jingui [Journal of Materials Chemistry C, 2014, vol. 2, # 4, p. 614 - 617]
[54]Sayer, James R.; Walldn, Karin; Pesnot, Thomas; Campbell, Frederick; Gane, Paul J.; Simone, Michela; Koss, Hans; Buelens, Floris; Boyle, Timothy P.; Selwood, David L.; Waksman, Gabriel; Tabor, Alethea B. [Bioorganic and Medicinal Chemistry, 2014, vol. 22, # 22, p. 6459 - 6470]
[55]Özdemir, Zeynep; Karakurt, Arzu; Çaliş, Ünsal; Gü.nal, Selami; Işik, Şamil; Şahin, Z. Sibel; Dalkara, Sevim [Medicinal Chemistry, 2015, vol. 11, # 1, p. 41 - 49]
[56]Ma, Liang; Wang, Taijin; Shi, Min; Ye, Haoyu [Drug Design, Development and Therapy, 2016, vol. 10, p. 1807 - 1815]
[57]Chen, Jianzhong; Zhang, Zhenfeng; Liu, Delong; Zhang, Wanbin [Angewandte Chemie - International Edition, 2016, vol. 55, # 29, p. 8444 - 8447][Angew. Chem., 2016, vol. 128, # 29, p. 8584 - 8587]
[58]Wei, Simin; Feng, Xiangqing; Du, Haifeng [Organic and Biomolecular Chemistry, 2016, vol. 14, # 34, p. 8026 - 8029]
[59]Current Patent Assignee: Institute of Chemistry (in: CAS); CHINESE ACADEMY OF SCIENCES - CN105669586, 2016, A Location in patent: Paragraph 0077
[60]Sari, Suat; Karakurt, Arzu; Uslu, Harun; Kaynak, F. Betül; Çalış, Ünsal; Dalkara, Sevim [European Journal of Medicinal Chemistry, 2016, vol. 124, p. 407 - 416]
[61]Current Patent Assignee: F2G LTD - WO2017/9651, 2017, A1 Location in patent: Page/Page column 64
[62]Gao, Wenchao; Lv, Hui; Zhang, Xumu [Organic Letters, 2017, vol. 19, # 11, p. 2877 - 2880]
[63]Günther, Marcel; Lategahn, Jonas; Juchum, Michael; Döring, Eva; Keul, Marina; Engel, Julian; Tumbrink, Hannah L.; Rauh, Daniel; Laufer, Stefan [Journal of Medicinal Chemistry, 2017, vol. 60, # 13, p. 5613 - 5637]
[64]Gundala, Trivikram Reddy; Godugu, Kumar; Nallagondu, Chinna Gangi Reddy [Journal of the Chinese Chemical Society, 2017, vol. 64, # 12, p. 1408 - 1416]
[65]Zhu, Menghua; Chen, De; Zeng, Sheng; Xing, Chenhu; Deng, Wei; Xiang, Jiannan; Wang, Rui-Jia [Tetrahedron Letters, 2018, vol. 59, # 33, p. 3214 - 3219]
[66]Yang, Yuwen; Yang, Weibo [Chemical Communications, 2018, vol. 54, # 86, p. 12182 - 12185]
[67]Current Patent Assignee: CHINA PHARMACEUTICAL UNIVERSITY - CN109320458, 2019, A Location in patent: Paragraph 0201; 0202; 0203
[68]Acar, Mustafa F.; Sari, Suat; Dalkara, Sevim [Drug Development Research, 2019, vol. 80, # 5, p. 606 - 616]
[69]Yang, Lixin; Liu, Yongqing; Fan, Minghua; Zhu, Guiwang; Jin, Hongwei; Liang, Jing; Liu, Zhenming; Huang, Zhuo; Zhang, Liangren [European Journal of Medicinal Chemistry, 2019, vol. 182]
[70]Bangalore, Pavan K.; Vagolu, Siva K.; Bollikanda, Rakesh K.; Veeragoni, Dileep K.; Choudante, Pallavi C.; Misra, Sunil; Sriram, Dharmarajan; Sridhar, Balasubramanian; Kantevari, Srinivas [Journal of Natural Products, 2020, vol. 83, # 1, p. 26 - 35]
[71]Chen, Xiangyang; Hao, Jiping; Houk, K. N.; Li, Yingzi; Lou, Liguang; Quan, Haitian; Song, Bichao; Wang, Lu; Xia, Yuanzhi; Xie, Peipei; Xu, Zhongliang; Yang, Weibo [Journal of the American Chemical Society, 2020, vol. 142, # 22, p. 9982 - 9992]
[72]Eagon, Scott; Hammill, Jared T.; Sigal, Martina; Ahn, Kevin J.; Tryhorn, Julia E.; Koch, Grant; Belanger, Briana; Chaplan, Cory A.; Loop, Lauren; Kashtanova, Anna S.; Yniguez, Kenya; Lazaro, Horacio; Wilkinson, Steven P.; Rice, Amy L.; Falade, Mofolusho O.; Takahashi, Rei; Kim, Katie; Cheung, Ashley; Dibernardo, Celine; Kimball, Joshua J.; Winzeler, Elizabeth A.; Eribez, Korina; Mittal, Nimisha; Gamo, Francisco-Javier; Crespo, Benigno; Churchyard, Alisje; García-Barbazán, Irene; Baum, Jake; Anderson, Marc O.; Laleu, Benoît; Guy, R. Kiplin [Journal of Medicinal Chemistry, 2020, vol. 63, # 20, p. 11902 - 11919]
[73]Kang, Lei; Wang, Fang; Zhang, Jinlong; Yang, Huameng; Xia, Chungu; Qian, Jinlong; Jiang, Gaoxi [Organic Letters, 2021, vol. 23, # 5, p. 1669 - 1674]
[74]Kang, Lei; Zhang, Jinlong; Yang, Huameng; Qian, Jinlong; Jiang, Gaoxi [Synlett, 2021, vol. 32, # 8, p. 785 - 789]
[75]Gaykar, Rahul N.; George, Malini; Guin, Avishek; Bhattacharjee, Subrata; Biju, Akkattu T. [Organic Letters, 2021, vol. 23, # 9, p. 3447 - 3452]
[76]Lee, Jisue; Kim, Jae-Goo; Lee, Haena; Lee, Tae Hoon; Kim, Ki-Young; Kim, Hakwon [Pharmaceutics, 2021, vol. 13, # 3, p. 1 - 20]
[77]Bantzi, Marina; Augsburger, Fiona; Loup, Jérémie; Berset, Yan; Vasilakaki, Sofia; Myrianthopoulos, Vassilios; Mikros, Emmanuel; Szabo, Csaba; Bochet, Christian G. [Journal of Medicinal Chemistry, 2021, vol. 64, # 9, p. 6221 - 6240]
[78]Lv, Hao-Peng; Yang, Xiao-Peng; Wang, Bai-Lin; Yang, Hao-Di; Wang, Xing-Wang; Wang, Zheng [Organic Letters, 2021, vol. 23, # 12, p. 4715 - 4720]
[79]Tian, Jiangyan; Li, Wendian; Li, Ruihao; He, Lin; Lv, Hui [Chinese Chemical Letters, 2021, vol. 32, # 12, p. 4038 - 4040]
[80]Kim, Wansoo; Kim, Hun Young; Oh, Kyungsoo [Journal of Organic Chemistry, 2021, vol. 86, # 22, p. 15973 - 15991]
[81]Fu, Haigen; Lam, Heather; Emmanuel, Megan A.; Kim, Ji Hye; Sandoval, Braddock A.; Hyster, Todd K. [Journal of the American Chemical Society, 2021, vol. 143, # 25, p. 9622 - 9629]
[82]Nanubolu, Jagadeesh Babu; Reddy Singam, Maneesh Kumar; Sridhar Reddy, Maddi; Suresh, Vavilapalli; Suri Babu, Undamatla [Organic Letters, 2021, vol. 23, # 20, p. 7888 - 7893]
[83]Das, Sanju; Mandal, Tanumoy; De Sarkar, Suman [Advanced Synthesis and Catalysis, 2022, vol. 364, # 4, p. 755 - 765]
[84]Shen, Li-Wen; Wang, Zhen-Hua; You, Yong; Yuan, Wei-Cheng; Zhao, Jian-Qiang; Zhou, Ming-Qiang [Organic Letters, 2022, vol. 24, # 4, p. 1094 - 1099]
[85]Chen, Hong-Ru; Qin, Hua-Li; Shu, Tao; Tang, Haolin; Yang, Wen-Fei [Organic and Biomolecular Chemistry, 2022, vol. 20, # 17, p. 3506 - 3510]

5
[ 288-32-4 ]
[ 613-54-7 ]
[ 64212-22-2 ]

Yield	Reaction Conditions	Operation in experiment
92%	With lithium hydride In tetrahydrofuran at -5 - 0℃; for 12h;
65%	In 1,4-dioxane; methanol; diethyl ether 0 deg C, 3 h then r.t., 2 h;
62%	In N,N-dimethyl-formamide at 4 - 20℃;

55%	With triethylamine In acetonitrile for 4h; Ambient temperature;
	In N,N-dimethyl-formamide 1.) 0 deg C, 2 h, 2.) RT, overnight;
	In N,N-dimethyl-formamide
1.5 g	With potassium carbonate In tetrahydrofuran at 20℃; for 3h;	18.2 (2) Synthesis of 2-(1H-imidazol-1-yl)-1-(naphthalen-2-yl)ethyl-1-one Crude 2-bromo-1-(naphthalen-2-yl)ethan-1-one (2.49 g, 10 mmol)It was dissolved in 50 ml of tetrahydrofuran with imidazole (1.36 g, 20 mmol).Add potassium carbonate (2.76 g, 20 mmol), stir at room temperature for 3 h,The reaction solution was removed in vacuo, water was added andEtOAc was evaporated.The organic phase was washed with water and brine, dried over anhydrous sodium sulfate.Spin-drying, separation by silica gel column chromatography (DCM: MeOH=100:1 v/v)1.5 g of a white solid were obtained in a yield of 75.1%.
	In N,N-dimethyl-formamide at 0 - 20℃;

Reference： [1]Lin, Chun Min; Wong, Fung Fuh; Huang, Jiann-Jyh; Yeh, Mou-Yung [Heterocycles, 2006, vol. 68, # 7, p. 1359 - 1370]
[2]Bennett; Mullen; Allen; Mitchell; St. Georgiev [Arzneimittel-Forschung/Drug Research, 1989, vol. 39, # 10, p. 1206 - 1208]
[3]Location in patent: scheme or table Calis, Uensal; Septioglu, Ebubekir; Aytemir, Mutlu Dilsiz [Arzneimittel-Forschung/Drug Research, 2011, vol. 61, # 6, p. 327 - 334]
[4]Wahbi, Y.; Caujolle, R.; Tournaire, C.; Payard, M.; Linas, M. D.; Seguela, J. P. [European Journal of Medicinal Chemistry, 1995, vol. 30, # 12, p. 955 - 962]
[5]Walker; Wallach; Hirschfeld [Journal of Medicinal Chemistry, 1981, vol. 24, # 1, p. 67 - 74]
[6]Karakurt, Arzu; Alagöz, Mehmet A.; Sayoǧlu, Burcu; Çalş, Ünsal; Dalkara, Sevim [European Journal of Medicinal Chemistry, 2012, vol. 57, p. 275 - 282]
[7]Current Patent Assignee: CHINA PHARMACEUTICAL UNIVERSITY - CN109320458, 2019, A Location in patent: Paragraph 0201; 0204; 0205
[8]Acar, Mustafa F.; Sari, Suat; Dalkara, Sevim [Drug Development Research, 2019, vol. 80, # 5, p. 606 - 616]

6
[ 616-47-7 ]
[ 613-54-7 ]
[ 121704-58-3 ]

Yield	Reaction Conditions	Operation in experiment
93%	In acetonitrile at 80℃; for 12h;	20 Example 20 Preparation of 3-acetonaphthyl-1-methylimidazolium (1s) Example 20 Preparation of 3-acetonaphthyl-1-methylimidazolium (1s) [0187] [0188] After 2-bromo-2-acetonaphthone (10a, 2.49 g, 10 mmol) was dissolved in acetonitrile (50 mL), methylimidazole (11a, 0.836 mL, 10.5 mmol) was added thereto. The mixture was stirred for 12 hours in the heating condition of 80° C. Once the reaction was terminated, the reaction solvent was removed under a reduced pressure. Subsequently, column chromatography (10% methanol/dichloromethane) was performed to obtain a desired compound, 3-acetonaphthyl-1-methylimidazolium (1s, 3.08 g, 93%). [0189] 1H NMR (500 MHz, CDCl3) δ 4.02 (s, 3H), 6.15 (s, 2H), 7.68 (m, 4H), 7.99 (m, 4H), 8.74 (s, 1H), 9.01 (s, 1H); [0190] 13C NMR (125 MHz, CDCl3) δ 191.3, 139.5, 137.7, 134.0, 132.5, 130.9, 130.5, 130.0, 129.4, 129.0, 128.7, 125.4, 124.6, 124.3, 56.3, 36.8
73%	In ethanol at 0 - 20℃;
	In acetonitrile Ambient temperature;

In ethanol

Reference： [1]Current Patent Assignee: FUTURECHEM CO LTD - US2014/194620, 2014, A1 Location in patent: Paragraph 0187-0190
[2]Hubbard, Sarah C.; Jones, Paul B. [Tetrahedron, 2005, vol. 61, # 31, p. 7425 - 7430]
[3]Dominianni, Samuel J.; Yen, Terence T. [Journal of Medicinal Chemistry, 1989, vol. 32, # 10, p. 2301 - 2306]
[4]Location in patent: experimental part Zhu, Xiaohe; Li, Weipeng; Yan, Hong; Zhong, Rugang [Journal of Photochemistry and Photobiology A: Chemistry, 2012, vol. 241, p. 13 - 20]

7
[ 613-54-7 ]
[ 91571-04-9 ]

Yield	Reaction Conditions	Operation in experiment
85%	With sodium tetrahydroborate In methanol at 0 - 20℃; for 1h;
84%	With zirconocene dichloride; (dimethoxy)methylsilane; diethylamine In toluene at 23℃; Inert atmosphere;
	With sodium tetrahydroborate In methanol at 20℃;

	With sodium tetrahydroborate In methanol
	With sodium tetrahydroborate Inert atmosphere;
	With methanol; sodium tetrahydroborate at 0 - 20℃; for 2.16667h; Inert atmosphere;
	With methanol; sodium tetrahydroborate

Reference： [1]Hiratake, Jun; Inagaki, Minoru; Nishioka, Takaaki; Oda, Jun'ichi [Journal of Organic Chemistry, 1988, vol. 53, # 26, p. 6130 - 6133]
[2]Kehner, Rebecca A.; Hewitt, Matthew Christian; Bayeh-Romero, Liela [ACS Catalysis, 2022, vol. 12, # 3, p. 1758 - 1763]
[3]Taşdemir, Volkan; Kalay, Erbay; Dertli, Enes; Şahin, Engin [Biocatalysis and Biotransformation, 2020, vol. 38, # 6, p. 438 - 444]
[4]Baydaş, Yasemin; Kalay, Erbay; Şahin, Engin [Biocatalysis and Biotransformation, 2022, vol. 40, # 1, p. 29 - 37]
[5]Sawada, Erika; Nakata, Kenya [Chemistry Letters, 2021, vol. 50, # 2, p. 371 - 373]
[6]Tian, Xianhai; Karl, Tobias A.; Reiter, Sebastian; Yakubov, Shahboz; de Vivie-Riedle, Regina; König, Burkhard; Barham, Joshua P. [Angewandte Chemie - International Edition, 2021, vol. 60, # 38, p. 20817 - 20825][Angew. Chem., 2021, vol. 133, # 38, p. 20985 - 20993]
[7]Özdemir, Akın; Şahin, Engin [Chirality, 2022, vol. 34, # 5, p. 796 - 806]

8
[ 613-54-7 ]
[ 38061-36-8 ]

Yield	Reaction Conditions	Operation in experiment
	With hydrogenchloride; hexamethylenetetramine 1.) CHCl₃, reflux, 4 h, 2.) ethanol, room temp., 16 h; Yield given. Multistep reaction;
	With hydrogenchloride; hexamethylenetetramine 1) CHCl₃, reflux, 4 h, 2) ethanol, room temperature, 16 h; Multistep reaction;
	Stage #1: 2-Bromo-2'-acetonaphthone With hexamethylenetetramine In chloroform at 50℃; for 2h; Stage #2: With hydrogenchloride In ethanol; water monomer at 50℃; for 2h;

Reference： [1]Calis; Dalkara; Ertan; Sunal [Archiv der Pharmazie, 1988, vol. 321, # 12, p. 841 - 846]
[2]Calis; Dalkara; Ertan [Arzneimittel-Forschung/Drug Research, 1992, vol. 42, # 5, p. 592 - 594]
[3]Cui, Yating; Gou, Wenfeng; Hou, Wenbin; Li, Yiliang; Luo, Lingling; Shang, Haihua; Sun, Tiemin; Sun, Xiao; Yu, Jiang [Journal of Enzyme Inhibition and Medicinal Chemistry, 2022, vol. 37, # 1, p. 952 - 972]

9
[ 613-54-7 ]
[ 100306-23-8 ]
[ 85554-14-9 ]

Yield	Reaction Conditions	Operation in experiment
	With Daucus carota roots; In water; at 30℃; for 40.0h;	General procedure: alpha-Bromoketones (1.0 mmol) were added to a suspension of freshly cut D. carota roots (17 g) in 100 mL of distilled water and the reaction mixtures were incubated in an orbital shaker (150 rpm) at 30 C. The progress of the reaction was monitored by TLC or by GC. After completion of the reaction, the suspensions were filtered off and the carrot root was washed successively with water. Filtrates were extracted with ethyl acetate (3 × 30 mL), dried on anhydrous MgSO4 and concentrated under reduced pressure. The crude products were purified by column chromatography on silica gel using ethyl acetate/n-hexane gradient to give the desired products in high purity.

Reference： [1]Journal of Organometallic Chemistry,1985,vol. 290,p. C23 - C26
[2]Journal of Organic Chemistry,1983,vol. 48,p. 1784 - 1786
[3]Journal of Organic Chemistry,1985,vol. 50,p. 1384 - 1394
[4]Tetrahedron Asymmetry,2006,vol. 17,p. 1036 - 1040
[5]Journal of the Iranian Chemical Society,2019,vol. 16,p. 583 - 591
[6]Biocatalysis and Biotransformation,2020

10
[ 613-54-7 ]
[ 93-08-3 ]

Yield	Reaction Conditions	Operation in experiment
100%	With sodium hydroxide In benzene
98%	With sodium dihydrosulfite; potassium carbonate In lithium hydroxide monohydrate; toluene at 35℃; for 3h;
98%	With tris-(trimethylsilyl)silane In acetonitrile for 24h; Schlenk technique; Inert atmosphere; Irradiation;

98%	With Hantzsch ester; N-ethyl-N,N-diisopropylamine In lithium hydroxide monohydrate at 20℃; for 8h; Irradiation; Inert atmosphere;
98%	With Hantzsch ester; sulforhodamine 101; N-ethyl-N,N-diisopropylamine; Eosin In lithium hydroxide monohydrate at 20℃; for 8h; Irradiation; Inert atmosphere;
94%	With potassium carbonate; butan-1-ol at 100℃;
91%	With Hantzsch ester In 2,2,2-trifluoroethanol at 20℃; for 4h; UV-irradiation; Sealed tube; Green chemistry;
89%	With Hantzsch ester; glacial acetic acid for 1h; Irradiation; Inert atmosphere;	Reduction of α-Haloketones 2; General Procedure General procedure: Into a flask charged with the respective α-haloketone 2 (1 mmol) and ethidine (Hantzsch's ester, 1a; 1.2 mmol), was added the solvent as per Tables 2-4 (2.5 mL). The flask was then attached to a balloon filled with N2 and irradiated with 3 W blue LED at a distance of 5 cm. The workup was followed when TLC showed that ethidine or the haloketone was consumed. When AcOH was used as the solvent, the reaction was worked up as follows: the reaction mixture was partitioned between EtOAc (40 mL) and H2O (10 mL), then the organic phase was washed with sat. aq NaHCO3 (3 15 mL) and brine (15 mL), and dried (anhyd Na2SO4). After concentration under reduced pressure, the residue was subjected to flash chromatography for purification eluting with petroleum ether (PE) and CH2Cl2. When aprotic polar solvents were used, the reaction mixture was diluted with EtOAc (40 mL) and the organic layer was washed with H2O (3 15 mL) and brine (15 mL), and dried (anhyd Na2SO4). When volatile solvents were used, the mixture was concentrated under reduced pressure and the residue was subjected to flash chromatography for purification.
87%	With lithium hydroxide monohydrate; triphenylantimony at 120℃; for 0.166667h; Microwave irradiation;
84%	With tris(2,2′-bipyridyl)ruthenium(II) chloride; 1,5-dimethoxynaphthalene; L-ascorbic acid In methanol; lithium hydroxide monohydrate for 12h; Inert atmosphere; Irradiation;
84%	With diethyl ether In lithium hydroxide monohydrate at 20℃; for 1.5h; Schlenk technique; Irradiation;	3. General procedure for the reaction of reductive dehalogenation General procedure: To a 10 mL schlenk tube, 1 (0.2 mmol), H2O (1.6 mmol) and Et2O (4 mL) were added in sequence. The reaction mixture was stirred and irradiated by 40 W Kessil purple LED (390 nm) at room temperature . After the reaction was completed, the reaction mixture was purified by flash column chromatography using PE/EtOAc as the eluent to give the desired product.
81%	With potassium fluoride; bis(triphenyltin) selenide In acetonitrile for 24h; Ambient temperature;
79%	With cesium lead bromide; N-ethyl-N,N-diisopropylamine In dichloromethane at 20℃; for 12h; Irradiation;
79 %Spectr.	With Hantzsch ester In acetonitrile at 20℃; for 24h; Irradiation;
	Multi-step reaction with 2 steps 1: N,N,N-tributyl-1-butanaminium iodide; potassium carbonate / dichloromethane; lithium hydroxide monohydrate / 20 °C 2: bis[(2,2,2-trifluoroacetyl)oxy]palladium; 5,5'-bis[di(3,5-di-t-butyl-4-methoxyphenyl)phosphino]-4,4'-bi-1,3-benzodioxole; hydrogen / propan-2-one / 24 h / 20 °C / 22502.3 Torr / Glovebox; Autoclave
	Multi-step reaction with 2 steps 1: potassium carbonate / propan-2-one / Reflux 2: 4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl-4',4',5',5'-tetramethyl-1,3,2-dioxaborolane; sodium tertiary butoxide; 2,6-bis[1-(2,6-dimethylphenylimino)ethyl]pyridine cobalt(II)dichloride / tetrahydrofuran; methanol / 3 h / 65 °C / Schlenk technique; Inert atmosphere
50 %Spectr.	With Hantzsch ester; N-ethyl-N,N-diisopropylamine In lithium hydroxide monohydrate at 20℃; for 2h; Irradiation; Inert atmosphere;

Reference： [1]Brown; Dyson; Ellis; Welton [Chemical Communications, 2001, # 18, p. 1862 - 1863]
[2]Park, Kwanghee Koh; Lee, Chul Woo; Oh, Si-Young; Park, Joon Woo [Journal of the Chemical Society. Perkin transactions I, 1990, # 8, p. 2356 - 2357]
[3]Jiang, Hao; Bak, Jesper R.; Lopez-Delgado, Francisco Javier; Jorgensen, Karl Anker [Green Chemistry, 2013, vol. 15, # 12, p. 3355 - 3359]
[4]Li, Xinglong; Wang, Ying; Song, Ao; Zhang, Minghui; Chen, Mengning; Jiang, Man; Yu, Shengsheng; Wang, Rongzhou; Xing, Lingbao [Chinese Journal of Chemistry, 2021, vol. 39, # 10, p. 2725 - 2730]
[5]Jiang, Man; Li, Xing-Long; Liu, Hui; Wang, Rong-Zhou; Wang, Ying; Xing, Ling-Bao; Yu, Shengsheng; Zhang, Ming-Hui [Dyes and Pigments, 2022, vol. 197]
[6]Chen, Jingbo; Zhang, Yushun; Yang, Liquan; Zhang, Xiang; Liu, Jianping; Li, Liang; Zhang, Hongbin [Tetrahedron, 2007, vol. 63, # 20, p. 4266 - 4270]
[7]Jung, Jaehun; Kim, Jun; Park, Gyurim; You, Youngmin; Cho, Eun Jin [Advanced Synthesis and Catalysis, 2016, vol. 358, # 1, p. 74 - 80]
[8]Lu, Zheng; Yang, Yong-Qing [Synthesis, 2019, vol. 51, # 2, p. 508 - 515]
[9]Murata, Yuki; Sugawara, Yoshiyuki; Matsumura, Mio; Kakusawa, Naoki; Yasuike, Shuji [Chemical and Pharmaceutical Bulletin, 2017, vol. 65, # 11, p. 1081 - 1084]
[10]Maji, Tapan; Karmakar, Ananta; Reiser, Oliver [Journal of Organic Chemistry, 2011, vol. 76, # 2, p. 736 - 739]
[11]Chen, Jiajia; Chen, Jianhui; Luo, Yanshu; Xia, Yuanzhi; Zhang, Jinrong [Tetrahedron Letters, 2022]
[12]Schultz, Erwin K. V.; Harpp, David N. [Synthesis, 1998, # 8, p. 1137 - 1140]
[13]Zhu, Xiaolin; Lin, Yixiong; Sun, Yue; Beard, Matthew C.; Yan, Yong [Journal of the American Chemical Society, 2019, vol. 141, # 2, p. 733 - 738]
[14]Luo, Jian; Zhang, Xiang; Zhang, Jian [ACS Catalysis, 2015, vol. 5, # 4, p. 2250 - 2254]
[15]Chen, Jianzhong; Zhang, Zhenfeng; Liu, Delong; Zhang, Wanbin [Angewandte Chemie - International Edition, 2016, vol. 55, # 29, p. 8444 - 8447][Angew. Chem., 2016, vol. 128, # 29, p. 8584 - 8587]
[16]Gao, Kecheng; Xu, Man; Cai, Cheng; Ding, Yanghao; Chen, Jianhui; Liu, Bosheng; Xia, Yuanzhi [Organic Letters, 2020, vol. 22, # 15, p. 6055 - 6060]
[17]Bai, Zhihang; Hu, Xiao-Yu; Tian, Xueqi; Velmurugan, Krishnasamy; Wang, Kaiya; Zuo, Minzan [Beilstein Journal of Organic Chemistry, 2022, vol. 18, p. 429 - 437]

11
[ 75-18-3 ]
[ 613-54-7 ]
[ 6267-01-2 ]

Yield	Reaction Conditions	Operation in experiment
92%	In acetone	4.1 2.4.1 Synthesis of [(Me)₂SCH₂C(O)C₁₀H₇]Br (1) To an acetone solution (10 mL) of dimethyl sulfide (0.062 g, 1.0 mmol) was added 2-bromo-2ʹ-naphtyl acetophenone (C10H7C(O)CH2Br) (0.249 g, 1.0 mmol) and the mixture was stirred for 5 h. The light solid product (sulfonium salt) was isolated by filtration and was washed with acetone several times and dried under reduced pressure. Yield:0.293 g (92%). Anal.Calc. for C14H14BrOS(%): C, 35.36; H, 3.56; S, 9.53; Found: C, 35.43; H, 3.65; S, 9.32. M. p. 193-194 °C.IR (KBr disk): ν/cm-11665 (CO)·1H NMR (DMSO-d6,ppm):δ 2.99 (s, 6H, S(CH3)2); 5.60 (s, 1H, CH); 7.67-8.77 (m, 7H, Ar). 13C NMR (DMSO-d6,ppm):δ25.23 (s, S(CH3)2); 53.49(s, CH); 122.49-135.80(Ar); 192.18(s, CO).
80%	In ethanol for 0.5h; Heating;
	at 0 - 20℃; Inert atmosphere;

	In acetone for 12h;
	In acetone at 20℃; for 48h; Sealed tube;

Reference： [1]Sabounchei, Seyyed Javad; Sedghi, Asieh; Bayat, Mehdi; Hosseinzadeh, Marjan; Hashemi, Ali; Yousefi, Abed; Gable, Robert W. [Journal of Molecular Structure, 2019, vol. 1175, p. 346 - 356]
[2]Abdelhamid, Abdou O.; Al-Hamidi, Abdulaziz A. [Journal of the Chinese Chemical Society, 1995, vol. 42, # 1, p. 83 - 88]
[3]Location in patent: experimental part Kantam, M. Lakshmi; Mahendar, Koosam; Sreedhar, Bojja; Choudary, Boyapati. M.; Bhargava, Suresh K.; Priver, Steven H. [Tetrahedron, 2010, vol. 66, # 27-28, p. 5042 - 5052]
[4]Yuan, Zhenbo; Fang, Xinxin; Li, Xuanyi; Wu, Jie; Yao, Hequan; Lin, Aijun [Journal of Organic Chemistry, 2015, vol. 80, # 21, p. 11123 - 11130] He, Xinwei; Xie, Mengqing; Tang, Qiang; Zuo, Youpeng; Li, Ruxue; Shang, Yongjia [Journal of Organic Chemistry, 2019, vol. 84, # 18, p. 11623 - 11638]
[5]Kang, Xiaokang; Liang, Xiayu; Zeng, Qingle [Organic Letters, 2021, vol. 23, # 19, p. 7477 - 7481]

12
[ 288-88-0 ]
[ 613-54-7 ]
[ 89082-09-7 ]

Yield	Reaction Conditions	Operation in experiment
52.1%	With triethylamine In acetone at -10 - 20℃;
21%	With triethylamine In acetonitrile for 4h; Ambient temperature;
	With sodium In methanol for 6h; Heating;

	With triethylamine In acetone Reflux;
	With sodium In methanol at 70℃; Microwave irradiation;
	With potassium carbonate In acetonitrile at 40 - 80℃; for 21h;	9 4.3.2. Procedure for the synthesis of triazoaryl aminocycloalkanols 1r-1u, 3 General procedure: To a mixture of potassium carbonate (1.5 mmol), 1,2,3- and 1,2,4-triazole (1 mmol) and 5 mL of acetonitrile at 40°C was added a solution of α-bromo alkanones (1.0 mmol) in 5 ml of acetonitrile. The mixture was allowed to react for 5 h at 40°C and then at reflux temperature (80°C) for 16 h. The solid was removed by filtration and the filtrate was concentrated to dryness leaving a residue. This was dissolved in dichloromethane and washed twice with water. The organic extract was dried over sodium sulfate and purified by column chromatography (60-75% yield).13

Reference： [1]Location in patent: experimental part Yamada, Kazuhiro; Yoshizawa, Yuko; Oh, Keimei [Molecules]
[2]Wahbi, Y.; Caujolle, R.; Tournaire, C.; Payard, M.; Linas, M. D.; Seguela, J. P. [European Journal of Medicinal Chemistry, 1995, vol. 30, # 12, p. 955 - 962]
[3]Oezkanli, Fuegen; Gueney, Ahu; Calis, Uensal; Uzbay, Tayfun [Arzneimittel-Forschung/Drug Research, 2003, vol. 53, # 11, p. 758 - 762]
[4]Location in patent: experimental part Roman, Gheorghe; Vlahakis, Jason Z.; Vukomanovic, Dragic; Nakatsu, Kanji; Szarek, Walter A. [ChemMedChem, 2010, vol. 5, # 9, p. 1541 - 1555]
[5]Sari, Suat; Karakurt, Arzu; Uslu, Harun; Kaynak, F. Betül; Çalış, Ünsal; Dalkara, Sevim [European Journal of Medicinal Chemistry, 2016, vol. 124, p. 407 - 416]
[6]Vyas, Vijyesh K.; Bhanage, Bhalchandra M. [Tetrahedron Asymmetry, 2017, vol. 28, # 7, p. 974 - 982]

13
[ 45529-92-8 ]
[ 613-54-7 ]
2-(2-Imino-4,5-dimethyl-oxazol-3-yl)-1-naphthalen-2-yl-ethanone [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
74%	In tetrahydrofuran; acetonitrile for 24h; Ambient temperature;

Reference： [1]Mekonnen, Belew; Crank, George; Craig, Donald [Journal of Heterocyclic Chemistry, 1997, vol. 34, # 2, p. 589 - 599]

14
[ 35629-70-0 ]
[ 613-54-7 ]
2-(2-Imino-4-methyl-oxazol-3-yl)-1-naphthalen-2-yl-ethanone [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
13%		Example 3 - Synthesis of 3-methvI-6-(2'-naphthyl)imidazo[2,l-bloxazole (Compound 24); See J. Heterocyclic Chem., 1997, 34, 589-599; A. Preparation of 2-imino-4-methyl-3-(2'-naphthacyl)-2,3-dihydrooxazole; A solution of 2-bromoacetylnaphthalene (889mg, 3.57mmol) in anhydrous THF (5mL) was added dropwise via cannula to a solution of <strong>[35629-70-0]2-amino-4-methyloxazole</strong> (350mg, 3.57mmol) in anhydrous acetonitrile (5mL) and the resultant solution allowed to stir under nitrogen for 16 hours. After this time, the precipitate which had formed was filtered and washed with cold acetonitrile. The solid was suspended in ice water and the pH adjusted to pH 12 with 2M aqueous ammonium hydroxide. The resultant yellow powder was filtered and washed with water. The powder was then suspended in toluene and concentrated in vacuo before being triturated with diethyl ether to give the title compound as a peach solid (127mg, 13%) after filtration. <n="24"/>1H NMR (300MHz, CDCl3) 8.81 (IH, s), 8.01-8.19 (5H, m), 7.70 (2H, quintet, J7.3 Hz), 7.27 (IH, s), 5.51 (2H, s), 1.95 (3H, , J 1.1 Hz).

Reference： [1]Journal of Heterocyclic Chemistry,1997,vol. 34,p. 589 - 599
[2]Patent: WO2009/13477,2009,A1 .Location in patent: Page/Page column 22-23

15
[ 62571-86-2 ]
[ 613-54-7 ]
2-captopril-2'-acetonaphthone [ No CAS ]

Reference： [1]Pharmaceutica Acta Helvetiae,1999,vol. 73,p. 303 - 306

16
[ 31374-18-2 ]
[ 613-54-7 ]
7-chloro-3-(2-naphthalen-2-yl-2-oxo-ethyl)-3<i>H</i>-quinazolin-4-one [ No CAS ]

Reference： [1]Revue Roumaine de Chimie,1999,vol. 44,p. 341 - 350

17
[ 93-08-3 ]
[ 13651-05-3 ]
[ 613-54-7 ]

Yield	Reaction Conditions	Operation in experiment
87%	With N-Bromosuccinimide; silica gel In methanol for 0.3h; Reflux; chemoselective reaction;	Typical experimental procedure General procedure: The α-bromination reaction was carried out using acetophenone (1200 mg, 10 mmol), N-bromosuccinimide (2136 mg, 12 mmol), 10% (w/w) silica gel (120mg) in 10 mL of methanol at reflux conditions until the disappearance of the substrate. (Note: 2136mg of N-bromosuccinimide was added portion wise i.e. 356 mg for each time in six portions). The progress of the reaction was monitored by TLC. The reaction mass was filtered after the completion of the reaction as per TLC and the catalyst was collected for reuse. The filtrate was concentrated under vacuum. Double distilled water was added to the reaction mixture and quenched with aqueous sodium thiosulfate and the product extracted with dichloromethane (Caution: Severe burning sensation of eyes was observed during the work-up process). The layers were separated and the organic layer was collected and washed thrice with distilled water (3×50mL). The collected organic layer was dried over anhydrous Na2SO4, filtered and concentrated. The obtained crude product was purified by column chromatography over silica gel (60-120 mesh) using n-hexane-EtOAc (99:1 ratio). With the aim of studying the recycling of the catalyst, the isolated catalyst was washed with ethyl acetate (5mL) after its filtration from the reaction medium, collected and dried in vacuum at 70°C to a constant weight. Subsequently it was reused for the α-bromination of acetophenone and achieved 95%, 86% and 83% yields of product (2a) for first, second and third reuse of catalyst respectively. All products gave spectroscopic data in agreement with the literature [15,21,27-30]. The method is also very practical for scale up in process development. We attempted large scale (100 gram scale) synthesis of 2-bromo-1-phenylethanone 2a and obtained fruitful results with isolated yields ranging from 93% to 96%.
1: 66% 2: 18%	With 1-methyl-3-(4-sulfonylbutyl)-1H-imidazol-3-ium trifluoromethanesulfonate; N-Bromosuccinimide at 55℃; for 0.333333h; Green chemistry;
86 % Spectr.	With N-Bromosuccinimide; trimethylsilyl trifluoromethanesulfonate In acetonitrile at 20℃; for 24h;

Reference： [1]Mohan Reddy, Bodireddy; Venkata Ramana Kumar, Velpula; Chinna Gangi Reddy, Nallagondu; Mahender Rao, Siripragada [Chinese Chemical Letters, 2014, vol. 25, # 1, p. 179 - 182]
[2]Vrazic, Dejan; Jereb, Marjan; Laali, Kenneth K.; Stavber, Stojan [Molecules, 2013, vol. 18, # 1, p. 74 - 96]
[3]Guha, Samar Kumar; Wu, Bo; Kim, Beom Soo; Baik, Woonphil; Koo, Sangho [Tetrahedron Letters, 2006, vol. 47, # 3, p. 291 - 293]

18
[ 613-54-7 ]
[ 34733-57-8 ]

Yield	Reaction Conditions	Operation in experiment
60%	With rongalite In N,N-dimethyl-formamide at 20℃; for 24h; Inert atmosphere;
54%	With titanium(IV) isopropylate; ethylmagnesium bromide In tetrahydrofuran; diethyl ether; water at 23℃; for 18h; Inert atmosphere;	Example Experimental Procedure General procedure: Ti(OiPr)4 (0.18 mL, 0.602 mmol) was added to a solution of 2-bromoacetophenone (4, 100. mg, 0.502 mmol) in THF (5 mL) atroom temperature. EtMgBr (0.47 mL, 1.41 mmol, 3 M in Et2O)was then added dropwise over 20 min during which the reactionmixture turned from clear to yellow to black. After 18 h,water (5 mL) was added, and the mixture was extracted EtOAc(3 × 5 mL). The combined organic layers were washed withbrine (1 × 10 mL), dried with MgSO4, and concentrated in vacuo.Purification by column chromatography (15% EtOAc/hexanes)afforded 1,4-diketone 8 as a white powder (47 mg, 79%).
15%	With 2,6-dimethylpyridine; cesium lead bromide; (5S)-5-benzyl-2,2,3-trimethylimidazolidin-4-one In N,N-dimethyl-formamide at 20℃; for 16h; Irradiation;

75 % Chromat.

With Tetrakis(dimethylamino)ethylen; iodine; magnesium sulfate In tetrahydrofuran at 67℃; for 0.5h;

Reference： [1]Chen, Jie; Hu, Wei; Wang, Min; Xu, Wen-Lei; Zhao, Wei-Ming; Zhou, Ling [Organic Letters, 2020, vol. 22, # 18, p. 7169 - 7174]
[2]Le, Nathan N.; Rodriguez, Aimee M.; Alleyn, James R.; Gesinski, Michael R. [Synlett, 2018, vol. 29, # 16, p. 2195 - 2198]
[3]Zhu, Xiaolin; Lin, Yixiong; Sun, Yue; Beard, Matthew C.; Yan, Yong [Journal of the American Chemical Society, 2019, vol. 141, # 2, p. 733 - 738]
[4]Nishiyama, Yutaka; Kobayashi, Akihiro [Tetrahedron Letters, 2006, vol. 47, # 31, p. 5565 - 5567]

19
[ 613-54-7 ]
[ 85554-14-9 ]

Reference： [1]Chemistry - A European Journal,2011,vol. 17,p. 14380 - 14384
[2]Biocatalysis and Biotransformation,2020
[3]Journal of Organic Chemistry,1988,vol. 53,p. 6130 - 6133

20
[ 874-33-9 ]
[ 613-54-7 ]
C₂₁H₂₁NO [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
		Step A: o-Tolualdehyde was converted to <strong>[874-33-9]methyl-(2-methyl-benzyl)-amine</strong> via reductive amination using aqueous methyl amine and NaBH4. <strong>[874-33-9]Methyl-(2-methyl-benzyl)-amin</strong>e was then alkylated with 2-bromo-2'-acetonaphthone followed by reduction by NaBH4 to give 2-[methyl-(2-methyl-benzyl)-amino]-1-naphthalen-2-yl-ethanol as a clear, light yellow oil: 1H NMR (300 MHz, CDCl3) delta 7.78-7.87 (m, 4 H), 7.40-7.51 (m, 3 H), 7.14-7.30 (m, 4 H), 4.89 (dd, J=10.1, 3.9 Hz, 1 H), 3.71 (d, J=12.9 Hz, 1 H), 3.54 (d, J=12.9 Hz, 1 H), 2.70 (dd, J=12.3, 10.3 Hz, 1 H), 2.62 (dd, J=12.4, 3.9 Hz, 1 H), 2.41 (s, 3 H), 2.35 (s, 3 H); Cl MS m/z 306 [C21H23NO+H]+.

Reference： [1]Patent: US2006/52378,2006,A1 .Location in patent: Page/Page column 111

21
[ 6665-86-7 ]
[ 613-54-7 ]
[ 1070399-41-5 ]

Reference： [1]Bioorganic and Medicinal Chemistry,2008,vol. 16,p. 7639 - 7645

22
[ 110-01-0 ]
[ 613-54-7 ]
[ 360554-36-5 ]

Yield	Reaction Conditions	Operation in experiment
80%	In acetone at 20℃; for 5h;
75%	In water; acetone at 0 - 20℃; for 2h;	8 Example 8. Synthesis of 1 -(2-naphthalen-2-yl-2-oxo-ethyl)-tetrahydro- thiophenium bromide.; [0047] To a solution of 2-bromo-2'-acetonaphthone (18.68 g, 75 mmol) in 100 ml_ of acetone and 4.1 ml_ of water at 00C was added tetrahydrothiophene (13.23 g, 150 mmol) dropwise. The resulting mixture was stirred at 00C for 1 hour before solid precipitated and was then stirred at room temperature for 1 hour. The resulting crude product was filtered through glass frit as solid and was washed by 100 ml_ of cold acetone. The crude product was recrystallized by 150 ml_ of ethanol to afford 19.0 g pure product at a yield of 75%. 1HNMR, d6-DMSO: 8.82 (s, 1 H), 8.17-7.98 (m, 4H), 7.78-7.65 (m, 2H), 5.63 (s, 2H), 3.64 (m, 4H), 2.40-2.29 (brm, 2h), 2.28-2.17 (brm, 2H).
	In acetone at 20℃; Inert atmosphere;	Typical procedure for the synthesis of 1-(2-oxo-2-phenylethyl)tetrahydro-1H-thiophen-1-ium tetraphenylborate (2a) General procedure: A mixture of phenacyl bromide (4.0 g, 20 mmol), acetone(200 mL), and tetrahydrothiophene (1.9 g, 22 mmol)in a flask (50 mL) was stirred at room temperature overnight. The resultingprecipitates were collected by filtration, washed withEt2O (10 mL × 3), and dried in vacuo to give phenacylthiolaniumbromide (5.592 g, 97% yield) as a white solid. To a beaker (300 mL) containinga clear solution obtained by dissolving this bromide in water (20 mL) andfiltering, a clear solution of na(6.673 g, 19.5 mmol) in water (20 mL) wasadded under stirring. The resulting mixture was treated with water (200 mL), andthe white precipiates were filtered, washed with water (50 mL × 3), and driedin vacuo to give 2a (10.0 g) in atotal yield of 95% starting from phenacyl bromide. For analysis, this productwas further purified by crystallization from EtOAc/CH3CN (100/27,v/v).

Reference： [1]Qin, Hongmei; Jia, Yimin; Wang, Na; Jiang, Zhong-Xing; Yang, Zhigang [Chemical Communications, 2020, vol. 56, # 59, p. 8265 - 8268] Wang, Na; Jia, Yimin; Qin, Hongmei; Jiang, Zhong-Xing; Yang, Zhigang [Organic Letters, 2020, vol. 22, # 18, p. 7378 - 7382]
[2]Current Patent Assignee: GOVERNMENT OF ABU DHABI; GlobalFoundries (in: Gov. of Abu Dhabi) - WO2009/91702, 2009, A1 Location in patent: Page/Page column 19
[3]Xu, Mei-Li; Huang, Wenhua [Tetrahedron Letters, 2014, vol. 55, # 30, p. 4230 - 4232]

23
[ 41789-95-1 ]
[ 613-54-7 ]
[ 1198790-42-9 ]

Yield	Reaction Conditions	Operation in experiment
100%		To a solution of alpha-bromo~2'-acetonaphthone (386.2 g, 1.57 mol) in dichloromethane (2.5 L) at 00C was added compound 3 (249.1 g, 1.65 mol) in 30 min, followed by the addition of triethylamine (220.7 mL, 1.57 mmol) in 45 min. After <n="25"/>stirring at 00C for 40 min, the reaction mixture was warmed to room temperature and stirred overnight. The reaction solution was then washed with water (2x) and the aqueous layer was re-extracted with dichloromethane (2x). The combined organic extract was dried over sodium sulfate and concentrated in vacuo. The ketone, compound 4, was obtained as a reddish oil (513.3 g, quantitative), was used in the next step without further purification: 'H NMR (CDCl3, 500 MHz) 8.50 (s, IH), 8.01(d, J= 8.5 Hz, IH), 7.92 (d, J = 8.0 Hz, IH), 7.88-7.85 (m, 2H)5 7.60-7.54 (m, 2H), 7.26-7.23 (m, IH), 6.97-6.94 (m, 2H), 6.82 (dd, J- 8.0, 2.5 Hz, IH), 3.88 (s, 2H), 3.75 (s, 3H), 3.69 (s, 2H), 2.42 (s, 3H); ESI MS m/z 320 [M+ H]+.
100%	With triethylamine; In dichloromethane; at 0 - 20℃; for 1.41667h;	To a solution of alpha-bromo-2?-acetonaphthone (386.2 g, 1.57 mol) in dichloromethane (2.5 L) at 0 C. was added compound 3 (249.1 g, 1.65 mol) in 30 min, followed by the addition of triethylamine (220.7 mL, 1.57 mmol) in 45 min. After stirring at 0 C. for 40 min, the reaction mixture was warmed to room temperature and stirred overnight. The reaction solution was then washed with water (2×) and the aqueous layer was re-extracted with dichloromethane (2×). The combined organic extract was dried over sodium sulfate and concentrated in vacuo. The ketone, compound 4, was obtained as a reddish oil (513.3 g, quantitative), was used in the next step without further purification: 1H NMR (CDCl3, 500 MHz) 8.50 (s, 1H), 8.01 (d, J=8.5 Hz, 1H), 7.92 (d, J=8.0 Hz, 1H), 7.88-7.85 (m, 2H), 7.60-7.54 (m, 2H), 7.26-7.23 (m, 1H), 6.97-6.94 (m, 2H), 6.82 (dd, J=8.0, 2.5 Hz, 1H), 3.88 (s, 2H), 3.75 (s, 3H), 3.69 (s, 2H), 2.42 (s, 3H); ESI MS m/z 320 [M+H]+

Reference： [1]Patent: WO2009/149258,2009,A2 .Location in patent: Page/Page column 19; 23-24
[2]Patent: US2014/275101,2014,A1 .Location in patent: Paragraph 0072; 0076; 0077
[3]Organic Process Research and Development,2016,vol. 20,p. 44 - 50

24
[ 67344-77-8 ]
[ 613-54-7 ]
[ 877264-90-9 ]

Yield	Reaction Conditions	Operation in experiment
		To a solution of compound 14 (23.1 g, 135.5 mmol) in methylene chloride (500 mL) was added alpha~bromo-2'-acetonapthone (27.9 g, 110.0 mmol) and the resulting mixture was stirred at 00C for 1 h prior to the addition of triethylamine (15.3 mL, 47.4 mmol). The reaction mixture was stirred at 00C for 2 h. The resulting mixture was diluted with water (200 mL) and the aqueous phase was extracted with additional methylene chloride (2 x 200 mL). The combined extracts were dried over sodium sulfate, filtered and concentrated to afford compound 15 (44.5 g) as a light yellow oil, which was used in the next step without further purification: 1H NMR (CDCl3, 500 MHz) 8.49 (s, IH), 8.01 (dd, J = 8.8, 1.8 Hz, IH), 7.95 (d, J- 8.0 Hz5 IH)5 7.90-7.84 (m, 2H), 7.62-7.52 (m, 3H), 7.40 (d, J= 8.0 Hz, IH), 7.31 (d, J- 8.0 Hz, IH), 7.19 (t, J= 7.7 Hz, IH), 3.91 (s, 2H), 3.68 (s, 2H), 2.40 (s, 3H).
44.5 g		To a solution of compound 14 (23.1 g, 115.5 mmol) in methylene chloride (500 mL) was added alpha-bromo-2?-acetonapthone (27.9 g, 110.0 mmol) and the resulting mixture was stirred at 0° C. for 1 h prior to the addition of triethylamine (15.3 mL, 47.4 mmol). The reaction mixture was stirred at 0° C. for 2 h. The resulting mixture was diluted with water (200 mL) and the aqueous phase was extracted with additional methylene chloride (2×200 mL). The combined extracts were dried over sodium sulfate, filtered and concentrated to afford compound 15 (44.5 g) as a light yellow oil, which was used in the next step without further purification: 1H NMR (CDCl3, 500 MHz) 8.49 (s, 1H), 8.01 (dd, J=8.8, 1.8 Hz, 1H), 7.95 (d, J=8.0 Hz, 1H), 7.90-7.84 (m, 2H), 7.62-7.52 (m, 3H), 7.40 (d, J=8.0 Hz, 1H), 7.31 (d, J=8.0 Hz, 1H), 7.19 (t, J=7.7 Hz, 1H), 3.91 (s, 2H), 3.68 (s, 2H), 2.40 (s, 3H)

Reference： [1]Patent: WO2009/149258,2009,A2 .Location in patent: Page/Page column 21; 49
[2]Patent: US2014/275101,2014,A1 .Location in patent: Paragraph 0072; 0147; 0148

25
[ 533-58-4 ]
[ 613-54-7 ]
C₁₈H₁₃IO₂ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
100%	With potassium carbonate In acetone at 80℃; for 4h;	General Procedure for the Synthesis of 1a General procedure: According to an adapted literature procedure, a 250 mL round bottom flask was charged with a magnetic stir bar, 2.189 g (11 mmol) 1- bromoacetophenone, 2.073 g (15 mmol) potassium carbonate, 2.200 g (10 mmol) of 2-iodophenol, and 100 mL of acetone. The reaction mixture was heated to reflux for 4 hours, and then cooled to room temperature. The reaction mixture was filtered through celite and the filtrate was concentrated to afford quantitative conversion to phenylpropan-2-ones as an off white solid. [1]
	With potassium carbonate In acetone Reflux;

Reference： [1]Zhu, Xiao-Rui; Deng, Chen-Liang [Synthesis, 2021, vol. 53, # 10, p. 1842 - 1848]
[2]Wang, Zhi-Qiang; Liang, Yun; Lei, Yong; Zhou, Ming-Bo; Li, Jin-Heng [Chemical Communications, 2009, # 35, p. 5242 - 5244]

26
[ 95-54-5 ]
[ 613-54-7 ]
[ 17286-69-0 ]

Yield	Reaction Conditions	Operation in experiment
96%	With 2,4,6-tripropyl-1,3,5,2,4,6-trioxatriphosphinane-2,4,6-trioxide In ethyl acetate at 0 - 20℃; for 5h;
96%	With Bronsted acidic ionic liquid supported on nano silica In neat (no solvent) at 20℃; for 0.5h; Green chemistry;	General Procedure for the Synthesis of 2-Arylquinoxalines (3a-h) General procedure: In 25 ml round-bottomed flask, a mixture of 1,2-phenylendiamine (1 mmol), a-bromoacetophenone(1 mmol) and BAILnano-SiO2 catalyst (35 mol%) was preparedand the reaction mixture was stirred at room temperature for the time shown inTable 2. The progress of the reaction was monitored by TLC. After completion of the reaction, ethyl acetate (5 mL) was added and the catalyst was separated by simplefiltration. The residue was dried over anhydrous Na2SO4 and after evaporation ofsolvent the pure product was obtained by recrystallization from ethanol.
91%	With fipronilβ-cyclodextrin In methanol; water at 70℃; for 2.2h;

89%	With cerium(III) chloride heptahydrate In poly(ethylene glycol)-400 at 20℃; for 0.5h;
84%	With sodium dodecyl-sulfate In water at 20℃;
	In water; N,N-dimethyl-formamide at 20℃; for 3h;
	With silica supported dodecatungstophosphoric acid In N,N-dimethyl-formamide at 90℃; Green chemistry;	General experimental procedure for the synthesis of quinoxalines General procedure: A mixture of phenacyl bromide (0.001 moles) and DTP/SiO2 (20 mole%) was stirred in10 ml DMF solvent at room temperature for 5 min. Then o-phenylenediamine(0.001 moles) was added slowly and the resultant mixture was stirred for 10 min atroom temperature and heated for a stipulated time. The completion of the reaction wasmonitored by TLC. After completion of the reaction, the reaction mixture was dilutedwith ethyl acetate (10 ml) and the catalyst was recovered by filtration. The filtrate waswashed with aqueous NaHCO3 and then with water followed by separation of aqueouslayer and organic layer. The organic layer is dried over anhydrous Na2SO4 and concentratedin a vacuum to give the crude product. The crude product was purified by crystallizationusing ethanol to afford the pure quinoxaline. The melting points of theproducts isolated in this study were found to be in good agreement with those reportedin the literature

Reference： [1]Harsha, Kachigere B.; Rangappa, Kanchugarkoppal S. [RSC Advances, 2016, vol. 6, # 62, p. 57154 - 57162]
[2]Daragahi, Seyed Arash Hosseini; Mohebat, Razieh; Mosslemin, Mohammad Hossein [Organic Preparations and Procedures International, 2018, vol. 50, # 3, p. 301 - 313]
[3]Location in patent: experimental part Madhav; Narayana Murthy; Prakash Reddy; Rama Rao; Nageswar [Tetrahedron Letters, 2009, vol. 50, # 44, p. 6025 - 6028]
[4]Location in patent: experimental part Wu, Fang-Wen; Hou, Rei-Sheu; Wang, Huey-Min; Kang, Iou-Jiun; Chen, Ling-Ching [Heterocycles, 2011, vol. 83, # 10, p. 2313 - 2320]
[5]Emmadi, Narender Reddy; Atmakur, Krishnaiah [Indian Journal of Chemistry - Section B Organic and Medicinal Chemistry, 2013, vol. 52, # 12, p. 1500 - 1504]
[6]Lai, Xiaojing; Qiu, Guanyinsheng; Ye, Qiuxiang; Wang, Ruixiang; Liu, Jin-Biao [Journal of Photochemistry and Photobiology A: Chemistry, 2020, vol. 386]
[7]Hebade, Madhav J.; Deshmukh, Tejshri R.; Dhumal, Sambhaji T. [Synthetic Communications, 2021, vol. 51, # 16, p. 2510 - 2520]

27
[ 106-95-6 ]
[ 613-54-7 ]
[ 1199941-51-9 ]

Yield	Reaction Conditions	Operation in experiment
88%	Stage #1: allyl bromide With zinc In tetrahydrofuran at 20℃; for 1h; Inert atmosphere; Stage #2: 2-Bromo-2'-acetonaphthone In tetrahydrofuran at 20℃; for 2h; Inert atmosphere;
77%	Stage #1: allyl bromide; 2-Bromo-2'-acetonaphthone With indium In tetrahydrofuran; water at 20℃; Stage #2: With sodium hydroxide In tetrahydrofuran; water at 20℃; for 2h;	6 General procedure for indium-mediated allylation reactions of α-bromoketones to form epoxides in one-pot General procedure: A mixture of allyl bromide (2.0mmol), indium powder (1.0mmol), and α-bromoketone (1.0mmol) 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. NaOH (2N) aqueous solution (2.5mL) was then added to the reaction mixture and the mixture was stirred at rt for 2h. 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 hexanes as eluent to give the product (162 mg, 77%). An oil; TLC (Et2O/hexanes (1:4)) Rf=0.57; 1H NMR (300 MHz, CDCl3) δ 2.73 (dd, J=15.0, 7.2 Hz, 1H), 2.84 (d, J=5.4 Hz, 1H), 3.00 (ddt, J=15.0, 7.2, 1.2 Hz, 1H), 3.07 (d, J=5.4 Hz, 1H), 5.06-5.19 (m, 2H), 5.74-5.88 (m, 1H), 7.43-7.50 (m, 3H), 7.80-7.85 (m, 4H); 13C NMR (75 MHz, CDCl3) δ 39.2 (CH2), 54.6 (CH2), 59.3 (C), 118.3 (CH2), 123.5 (CH), 124.8 (CH), 125.8 (CH), 126.0 (CH), 127.4 (CH), 127.7 (CH), 127.8 (CH), 132.5 (CH), 132.5 (C), 132.9 (C), 137.2 (C). These data are in agreement with those reported in the literature. 8a

Reference： [1]Zhang, Min; Hu, Yuanyuan; Zhang, Songlin [Chemistry - A European Journal, 2009, vol. 15, # 41, p. 10732 - 10735]
[2]Lin, Mei-Huey; Kuo, Chung-Kai; Lin, Wei-Cheng; Huang, Yen-Chih; Tsai, Yu-Ting; Liang, Kung-Yu; Li, Yi-Syuan; Chuang, Tsung-Hsun [Tetrahedron, 2013, vol. 69, # 38, p. 8263 - 8268]

28
[ 613-54-7 ]
[ 81-07-2 ]
[ 879346-60-8 ]

Yield	Reaction Conditions	Operation in experiment
96%	Stage #1: saccharin With sodium hydride In N,N-dimethyl-formamide Inert atmosphere; Stage #2: 2-Bromo-2'-acetonaphthone In N,N-dimethyl-formamide at 65℃; for 4h;	1.A The saccharin (25 g, 136 mmol) and DMF (350 mL) are introduced into a three-neck flask equipped with a thermometer and a condenser. The medium is inertized by a vacuum/nitrogen succession (3x) . Sodium hydride (6 g,150 mmol) is slowly added, followed by 2-bromo-l-(naphthalen-2-yl) ethanone (37.4 g, 150 mmol) . The reaction medium is heated to 65°C for 4 hours, and then cooled to room temperature. The formed precipitate is filtered, rinsed with water and dried until constant weight for obtained 37 g of the product IA. as a pale being solid (HPLC: RT = 4.97 min, 100%) . A second product batch is obtained by adding water into the filtrate. The formed precipitate is filtered, rinsed with water and then with a minimum of ethyl in order to obtain after drying, 10 g of product (HPLC: RT = 4.97 mm. 93s The global yield of this reaction is 9651H NMR, dmso-de, δ (ppm) : 5.62 (s, 2H) ; 7.68 (t, IH) ; 7.73 (t, IH) ; 8.00-8.25 (m, 7H) ; 8.39 (d, IH) ; 8.92 (s, IH) .Mass spectrum (ESI + ) : m/z 352 (MH+, 100%) ; 369 (MNH4+, 24%) .

Reference： [1]Current Patent Assignee: PIERRE FABRE PARCIPATIONS - WO2010/100139, 2010, A1 Location in patent: Page/Page column 26-27

29
[ 827-54-3 ]
[ 613-54-7 ]

Yield	Reaction Conditions	Operation in experiment
92%	With tris(2,2'-bipyridyl)ruthenium dichloride; Bromoform; [bis(acetoxy)iodo]benzene In 1,4-dioxane at 20℃; for 8h; Irradiation;	2.2 Representative procedure for the synthesis of α-bromoketone General procedure: Under conditions B: A 5 mL oven-dried reaction vessel equipped with a magnetic stirrer bar was charged withstyrene (1a, 20.8 mg, 0.20 mmol), Ru(bpy)3Cl2 (1.28 mg, 0.002 mmol, 1.0 mol%), PhI(OAc)2 (64.0 mg, 1.0 equiv.),CHBr3 (2b, 0.20 mmol) and dioxane (2.0 mL). The reaction vessel was exposed to blue LED (450-455 nm, 3 W) atroom temperature in air with stirring for 8 h. After completion of the reaction, the mixture was concentrated to yieldthe crude product, which was further purified by flash chromatography (silica gel, petroleum ether/ethyl acetate =10:1 to 5:1) to give the desired product 4a.
48%	With hydrogen bromide; oxygen In water; ethyl acetate for 7h; Irradiation;
35%	With dipotassium peroxodisulfate; potassium bromide In water at 60℃; for 12h; Green chemistry;

With 1,3-dibromo-5,5-dimethylimidazolidine-2,4-dione; water In acetone at 70℃; for 0.138833h;

10 Example 10 4 mmol (0.51 g) of naphthalene was dissolved in 10 mL of a 1/1 water/acetone solution (5 mL of water plus 5 mL of acetone mixed uniformly) to obtain a homogeneous solution A, which was added to the injected chestnut a; 8 mmol (2.29 g) of DBH was dissolved. lOmLl: 1 water / acetone solution (5ml water plus 5ml acetone mixed evenly), get homogeneous solution B, added to the injection chestnut b; 6mmol (0.91g) DBU and 6mmol (1.10g) pentafluorophenol dissolved In lOmL acetone (acetone), a homogeneous solution C was obtained, which was added to the injection pump c; the injection flow rate of the injected chestnut a and b was 0.3 ml/min, and the injection flow rate of the injected chestnut c was 0.5 ml/min; The reaction volume of the channel reactor is V = 5ml, the reaction time is 8.33min, the reaction volume of the second microchannel reactor is V = 5ml, the reaction time is 4.55min; the inner diameter of the first and second microchannel reactors is 0.5mm; the first microchannel reaction The temperature of the reactor was 70 ° C, the temperature of the second microchannel reactor was 70 ° C; after two cycles of the second microchannel reactor reaction, the reaction liquid was collected, and the product yield was calculated by HPLC method to be 77 %. After chromatography, the product 3 j is obtained.

Reference： [1]Wang, Zhihui; Wang, Lei; Wang, Zhiming; Li, Pinhua; Zhang, Yicheng [Chinese Chemical Letters, 2021, vol. 32, # 1, p. 429 - 432]
[2]Location in patent: experimental part Nobuta, Tomoya; Hirashima, Shin-Ichi; Tada, Norihiro; Miura, Tsuyoshi; Itoh, Akichika [Synlett, 2010, # 15, p. 2335 - 2339]
[3]Jiang, Qing; Sheng, Wenbing; Guo, Cancheng [Green Chemistry, 2013, vol. 15, # 8, p. 2175 - 2179]
[4]Current Patent Assignee: NANJING TECH UNIVERSITY - CN109824494, 2019, A Location in patent: Paragraph 0054-0055

30
[ 613-54-7 ]
[ 71365-99-6 ]

Yield	Reaction Conditions	Operation in experiment
94%	With potassium fluoride; CH₃O₃S^(1-)*C₂₇H₅₃N₂O₁₂⁽¹⁺⁾ In tert-Amyl alcohol at 100℃; for 1h;
93%	With C₂₄H₂₃N₂⁽¹⁺⁾*CH₃O₃S^(1-); cesium fluoride In acetonitrile at 100℃; for 2h;
88%	With Pentaethylene glycol; cesium fluoride In acetonitrile at 100℃; for 1.5h;

85%	With PSpentaEG; cesium fluoride In acetonitrile at 100℃; for 2.5h;
78%	With potassium fluoride; 2C₁₆H₃₆N⁽¹⁺⁾*C₂H₄O₆S₂^(2-) In water; <i>tert</i>-butyl alcohol at 90℃; for 4h;

Reference： [1]Jadhav, Vinod H.; Jeong, Hwan-Jeong; Lim, Seok Tae; Sohn, Myung-Hee; Kim, Dong Wook [Organic Letters, 2011, vol. 13, # 9, p. 2502 - 2505]
[2]Taher, Abu; Lee, Kyo Chul; Han, Hye Ji; Kim, Dong Wook [Organic Letters, 2017, vol. 19, # 13, p. 3342 - 3345]
[3]Jadhav, Vinod H.; Jang, Seung Ho; Jeong, Hwan-Jeong; Lim, Seok Tae; Sohn, Myung-Hee; Kim, Ju-Young; Lee, Sungyul; Lee, Ji Woong; Song, Choong Eui; Kim, Dong Wook [Chemistry - A European Journal, 2012, vol. 18, # 13, p. 3918 - 3924]
[4]Jadhav, Vinod H.; Jang, Seung Ho; Jeong, Hwan-Jeong; Lim, Seok Tae; Sohn, Myung-Hee; Chi, Dae Yoon; Kim, Dong Wook [Organic Letters, 2010, vol. 12, # 17, p. 3740 - 3743]
[5]Hammond, Gerald B.; Li, Wangbing; Lu, Zhichao; Xu, Bo [Organic Letters, 2021, vol. 23, # 24, p. 9640 - 9644]

31
[ 939-27-5 ]
[ 613-54-7 ]

Yield	Reaction Conditions	Operation in experiment
60%	With hydrogen bromide; oxygen In water; ethyl acetate at 20℃; for 24h; Irradiation;

Reference： [1]Tada, Norihiro; Ban, Kazunori; Hirashima, Shin-Ichi; Miura, Tsuyoshi; Itoh, Akichika [Organic and Biomolecular Chemistry, 2010, vol. 8, # 20, p. 4701 - 4704]

32
[ 34570-17-7 ]
[ 613-54-7 ]
[ 1210038-51-9 ]

Yield	Reaction Conditions	Operation in experiment
30%		Reference Example 1-1 2-Amino-5-(2-naphthyl)pyrrole-3-carboxamide (Reference compound Neo.1-1) Under ice-cooling, sodium ethoxide (2.7 g, 40 mmol) was added to a suspension of <strong>[34570-17-7]malonamamidine hydrochloride</strong> (5.5 g, 40 mmol) in dehydrated ethanol (130 mL), and then the mixture was stirred for 20 minutes. 2-Bromoacetylnaphthalene (5.0 g, 20 mmol) was added thereto, and the whole was stirred at room temperature overnight. The reaction mixture was concentrated in vacuo, and the obtained residue was purified by silica gel column chromatography to give the title reference compound (1.5 g) as a black solid (Yield 30%). 2-Amino-5-(2-naphthyl)pyrrole-3-carboxamide (Reference compound No.1-1) 1H-NMR (500 MHz, DMSO-d6) delta 5.77 (s, 2H), 6.86 (d, J = 2.7 Hz, 1H), 7.37 (m, 1H), 7.45 (m, 1H), 7.61 (dd, J = 8.7, 1.7 Hz, 1H), 7.75 (d, J = 7.9 Hz, 1H), 7.77-7.84 (m, 3H), 10.78 (s, 1H)

Reference： [1]Patent: EP2319831,2011,A1 .Location in patent: Page/Page column 9

33
[ 60827-45-4 ]
[ 613-54-7 ]
[ 1207291-20-0 ]
[ 1207291-19-7 ]

Yield	Reaction Conditions	Operation in experiment
	With toluene-4-sulfonic acid; In toluene; at 130℃;Product distribution / selectivity;	Example 23; Synthesis of (4S)-trans-,cis-2-(4-chlorophenyl)-2-bromomethyl-4-chloromethyl-1,3-dioxolane suppressing halogen exchange between substrates A mixture of 2-bromo-4'-chloroacetophenone (4.94 g, 2-chloro-4'-chloroacetophenone content=0.09%), p-toluenesulfonic acid monohydrate (0.20 g, 0.05 equivalent) and toluene (100 mL) was refluxed at 130C using an azeotropic distillation device with a Dean-Stark tube, and (S)-monochlorohydrin (2.59 g, 1.1 equivalents, >99%ee) was added dropwise under reflux such that the amount of the (S)-monochlorohydrin present in the reaction solution would be not more than 0.1 equivalent (not more than 2.1 mmol) relative to the amount of 2-bromo-4'-chloroacetophenone to be used (21.2 mmol), while analyzing the progress of the reaction by GC. After confirmation of the completion of the azeotropic distillation, the reaction mixture was cooled and washed with 10% aqueous sodium hydrogen carbonate solution and 10% brine. The solvent was evaporated under reduced pressure to give (4S)-trans-,cis-2-(4-chlorophenyl)-2-bromomethyl-4-chloromethyl-1,3-dioxolane (6.56 g, >99%ee). Here, the content percentage of (4S)-trans-,cis-2-(4-chlorophenyl)-2-chloromethyl-4-chloromethyl-1,3-dioxolane halogen-exchanged with a chlorine atom was 0.09%. Examples 30 to 41 Synthesis of (4S)-trans-cis-2-aryl-2-bromomethyl-4-chloromethyl-1,3-dioxolane suppressing halogen exchange In Examples 30 to 41, reactions were performed according to Example 23 and using aryl(bromomethyl)ketones (halogen-exchanged compound content<0.1%) shown in Table 7 and Table 8. The results are shown in Table 9 and Table 10 together with Example 23.

Reference： [1]Patent: EP2325178,2011,A1 .Location in patent: Page/Page column 28; 31

34
[ 14714-50-2 ]
[ 613-54-7 ]
[ 1329116-30-4 ]

Reference： [1]Heterocycles,2011,vol. 83,p. 1355 - 1361

35
[ 52749-50-5 ]
[ 613-54-7 ]
[ 1303566-75-7 ]

Yield	Reaction Conditions	Operation in experiment
85%	Stage #1: 3,4-dihydro-8-hydroxy-2(1H)-quinolinone With potassium carbonate In N,N-dimethyl-formamide at 20℃; for 0.5h; Stage #2: 2-Bromo-2'-acetonaphthone In N,N-dimethyl-formamide at 20℃; for 24h;

Reference： [1]Location in patent: experimental part Chen, Li-Chai; Chen, I-Li; Huang, Chih-Chiang; Liao, Chang-Hui; Chen, Jhy-Yih; Wang, Tai-Chi [Journal of the Chinese Chemical Society, 2010, vol. 57, # 6, p. 1331 - 1340]

36
[ 54197-66-9 ]
[ 613-54-7 ]
[ 1303566-72-4 ]

Yield	Reaction Conditions	Operation in experiment
91%		General procedure: 6-Hydroxyquinolin-2(1H)-one (3, 1.61 g, 10 mmol), K2CO3 (1.38 g, 10 mmol), and dry DMF (50 mL) were stirred at room temperature (r.t.) for 30 min. To this solution was added 2-(bromoacetyl)naphthalene (2.49 g, 10 mmol) in DMF (10 mL) in one portion. The resulting mixture was stirred continuously at r.t. for 24 h (TLC monitoring) and then poured into ice-water (100 mL). The white solid thus obtained was collected and crystallized from Et2O to give 9 (3.06 g, 93%).

Reference： [1]Journal of the Chinese Chemical Society,2010,vol. 57,p. 1331 - 1340
[2]European Journal of Medicinal Chemistry,2013,vol. 59,p. 227 - 234

37
[ 22246-18-0 ]
[ 613-54-7 ]
[ 1303566-73-5 ]

Yield	Reaction Conditions	Operation in experiment
95%		General procedure: 6-Hydroxyquinolin-2(1H)-one (3, 1.61 g, 10 mmol), K2CO3 (1.38 g, 10 mmol), and dry DMF (50 mL) were stirred at room temperature (r.t.) for 30 min. To this solution was added 2-(bromoacetyl)naphthalene (2.49 g, 10 mmol) in DMF (10 mL) in one portion. The resulting mixture was stirred continuously at r.t. for 24 h (TLC monitoring) and then poured into ice-water (100 mL). The white solid thus obtained was collected and crystallized from Et2O to give 9 (3.06 g, 93%).

Reference： [1]European Journal of Medicinal Chemistry,2013,vol. 59,p. 227 - 234
[2]Journal of the Chinese Chemical Society,2010,vol. 57,p. 1331 - 1340

38
[ 613-54-7 ]
5-(3-isothiocyanatophenyl)-1,3,4-oxadiazole-2-thiol [ No CAS ]
[ 1350301-99-3 ]

Yield	Reaction Conditions	Operation in experiment
78%	With triethylamine In acetone at 20℃; for 2h;	6.2. General procedure for the synthesis of S-substituted 1,3,4-oxadiazoles 12-19, 48-55 General procedure: To the stirred solution of 1,3,4-oxadiazole (4.2 mmol) and triethylamine (0.42 g, 4.2 mmol) in acetone (20 ml), one-portion solution of ω-phenacyl bromide (4.6 mmol) in acetone (5 ml) was added at room temperature. The reaction mixture was stirred for 2 h at room temperature (TLC control). The precipitate formed was filtered and washed with water and acetone. The same method was used for allyl bromide, benzyl chloride, methyl iodide.

Reference： [1]Location in patent: experimental part MacAev, Fliur; Ribkovskaia, Zinaida; Pogrebnoi, Serghei; Boldescu, Veaceslav; Rusu, Ghenadie; Shvets, Nathaly; Dimoglo, Anatholy; Geronikaki, Athina; Reynolds, Robert [Bioorganic and Medicinal Chemistry, 2011, vol. 19, # 22, p. 6792 - 6807]

39
[ 1147550-11-5 ]
[ 613-54-7 ]
[ 19339-62-9 ]

Yield	Reaction Conditions	Operation in experiment
98%	Stage #1: ammonium thiocyanate With montmorillonite K₁₀ clay In acetone at 20℃; for 0.666667h; Stage #2: 2-Bromo-2'-acetonaphthone at 20℃; for 0.00833333h; Neat (no solvent); Grinding;	General procedure for the preparation of K10-montmorillonite clay supported ammonium thiocyanate; General procedure for the synthesis of α-oxo thiocyanates by using K10-montmorillonite clay supported ammonium thiocyanate under catalyst and solvent free conditions In a round bottomed 500 ml flask equipped with stir bar and containing 100 ml acetone, was added 7.6 g of ammonium thiocyanate salt and stirred at room temperature until the complete dissolution of salt. To this clear solution, 10 g of montmorillonite K10 clay was added in portions over 10 min with stirring. After complete addition, the formation of reddish suspension was observed which was vigorously stirred for another 30 min at room temperature. Then the suspension is placed in a rotary vacuum evaporator and the solvent was removed under reduced pressure. The dry solid crust adhering to the walls of the flask was flaked off with a spatula, and solvent evaporation was resumed. After complete drying, yielded, about 17.6 g of clay supported ammonium thiocyanate as a light red free flowing powder which shows no loss of reactivity after standing in an open powder box for one week.; Phenacyl bromide (1 mmol) and K10-montmorillonite clay supported ammonium thiocyanate (3 mmol) were taken in mortar, mixed with spatula, and ground with pestle for stipulated time (see Table 3). After complete conversion as indicated by TLC, the solid reaction mixture was directly loaded on silica gel column by avoiding aqueous work up-extraction step. Later elution with ethyl acetate-hexane (9:1-3:1) solvent system and evaporation of solvents in rotary vacuum evaporator afforded pure phenacyl thiocyanate (99%). Same procedure as discussed above was followed to prepare all thiocyanate compounds shown in this work. All compounds prepared were characterized by IR, Mass, and NMR spectroscopy.

Reference： [1]Location in patent: experimental part Meshram; Thakur, Pramod B.; Madhu Babu; Bangade, Vikas M. [Tetrahedron Letters, 2012, vol. 53, # 14, p. 1780 - 1785]

40
[ 4026-18-0 ]
[ 613-54-7 ]
valic acid 2-naphthacyl ester [ No CAS ]

Reference： [1]Journal of Natural Products,2012,vol. 75,p. 425 - 431

41
[ 70500-72-0 ]
[ 613-54-7 ]
[ 1422390-39-3 ]

Yield	Reaction Conditions	Operation in experiment
43%		General procedure: 6-Hydroxyquinolin-2(1H)-one (3, 1.61 g, 10 mmol), K2CO3 (1.38 g, 10 mmol), and dry DMF (50 mL) were stirred at room temperature (r.t.) for 30 min. To this solution was added 2-(bromoacetyl)naphthalene (2.49 g, 10 mmol) in DMF (10 mL) in one portion. The resulting mixture was stirred continuously at r.t. for 24 h (TLC monitoring) and then poured into ice-water (100 mL). The white solid thus obtained was collected and crystallized from Et2O to give 9 (3.06 g, 93%).

Reference： [1]European Journal of Medicinal Chemistry,2013,vol. 59,p. 227 - 234

42
[ 19315-93-6 ]
[ 613-54-7 ]
[ 1422390-38-2 ]

Yield	Reaction Conditions	Operation in experiment
93%		General procedure: 6-Hydroxyquinolin-2(1H)-one (3, 1.61 g, 10 mmol), K2CO3 (1.38 g, 10 mmol), and dry DMF (50 mL) were stirred at room temperature (r.t.) for 30 min. To this solution was added 2-(bromoacetyl)naphthalene (2.49 g, 10 mmol) in DMF (10 mL) in one portion. The resulting mixture was stirred continuously at r.t. for 24 h (TLC monitoring) and then poured into ice-water (100 mL). The white solid thus obtained was collected and crystallized from Et2O to give 9 (3.06 g, 93%). M.p.: 220-221 C; 1H NMR (400 MHz, DMSO-d6): delta 5.74 (s, 2H, OCH2), 6.48 (d, J = 9.6 Hz, 1H-C(3)), 7.27-7.30 (m, 3H, Ar-H), 7.64-7.72 (m, 2H, Ar-H), 7.81 (d, J = 9.6 Hz, 1H-C(4)), 8.00-8.08 (m, 3H, Ar-H), 8.14 (d, J = 8.4 Hz, 1H, Ar-H), 8.77 (s, 1H, Ar-H), 11.67 (s, 1H, NH); 13C NMR (100 MHz, DMSO-d6): delta 70.61 (CH2O), 111.61, 116.41, 119.65, 119.94, 122.43, 123.36, 127.20, 127.84, 128.52, 128.97, 129.62, 129.89, 131.72, 132.15, 133.61, 135.35, 139.79, 152.89, 161.61 (C(2)), 194.43 (C=O). Anal. calcd. for C21H15NO3·0.1H2O: C 76.16, H 4.64, N 4.23; found: C 75.93, H 4.24, N, 4.25.

Reference： [1]European Journal of Medicinal Chemistry,2013,vol. 59,p. 227 - 234

43
[ 52749-50-5 ]
[ 613-54-7 ]
[ 1422390-27-9 ]

Yield	Reaction Conditions	Operation in experiment
	Stage #1: 3,4-dihydro-8-hydroxy-2(1H)-quinolinone With potassium carbonate In N,N-dimethyl-formamide at 20℃; for 0.5h; Stage #2: 2-Bromo-2'-acetonaphthone In N,N-dimethyl-formamide at 20℃; for 24h; Further stages;	5.1.7 N-(Naphthalen-2-yl)-2-(2-oxo-1,2-dihydroquinolin-6-yloxy)acetamide (15) General procedure: A solution of 9 (0.33 g, 1 mmol) in H2SO4 (3 mL) was stirred at r.t. for 10 min. To this solution, was added sodium azide (0.13 g, 2 mmol) in one portion. The mixture was stirred continuously at r.t. for 1 h (TLC monitoring) and then poured into ice-water (100 mL). The white solid thus obtained was collected and purified by flash column chromatography (FC; silica gel; CH2Cl2/EtOAc 5:1) and crystallized from CH2Cl2 to give 15 (0.28 g, 81%).

Reference： [1]Chen, I-Li; Chen, Jih-Jung; Lin, Yu-Chin; Peng, Ching-Tien; Juang, Shin-Hun; Wang, Tai-Chi [European Journal of Medicinal Chemistry, 2013, vol. 59, p. 227 - 234]

44
[ 52749-50-5 ]
[ 613-54-7 ]
[ 1303566-75-7 ]
[ 1422390-42-8 ]

Yield	Reaction Conditions	Operation in experiment
	Stage #1: 3,4-dihydro-8-hydroxy-2(1H)-quinolinone With potassium carbonate In N,N-dimethyl-formamide at 20℃; for 0.5h; Stage #2: 2-Bromo-2'-acetonaphthone In N,N-dimethyl-formamide at 20℃; for 24h; Overall yield = 91 %;	5.1.1 6-(2-Naphthalen-2-yl-2-oxoethoxy)quinolin-2(1H)-one (9) General procedure: 6-Hydroxyquinolin-2(1H)-one (3, 1.61 g, 10 mmol), K2CO3 (1.38 g, 10 mmol), and dry DMF (50 mL) were stirred at room temperature (r.t.) for 30 min. To this solution was added 2-(bromoacetyl)naphthalene (2.49 g, 10 mmol) in DMF (10 mL) in one portion. The resulting mixture was stirred continuously at r.t. for 24 h (TLC monitoring) and then poured into ice-water (100 mL). The white solid thus obtained was collected and crystallized from Et2O to give 9 (3.06 g, 93%).

Reference： [1]Chen, I-Li; Chen, Jih-Jung; Lin, Yu-Chin; Peng, Ching-Tien; Juang, Shin-Hun; Wang, Tai-Chi [European Journal of Medicinal Chemistry, 2013, vol. 59, p. 227 - 234]

45
[ 148638-23-7 ]
[ 613-54-7 ]
[ 1432481-86-1 ]

Yield	Reaction Conditions	Operation in experiment
79%	With pyridine In acetonitrile at 20℃; for 12h;	Synthesis of (4,4'-thiobis(3,5-diaryl-2,3-dihydrofuran-4,2-diyl))bis(arylmetha-nones) General procedure: A mixture of 2,2'-thiobis(1,3-diaryl-prop-2-en-1-ones) 1 (1 mmol) with α-phenacyl bromides 2 (2 mmol), pyridine 3 (2 mmol) and K2CO3 (2 mmol) in acetonitrile was stirred at room temperature for 12 h. The solid precipitated from the reaction mixture was filtered, washed with petroleum ether (2 ml) and recrystallized from dichloromethane-ethanol mixture (3:2(v/v), 5 ml) to give trans-(4,4'-thiobis(3,5-diaryl-2,3-dihydrofuran-4,2-diyl))bis(arylmethanones) 4 in good yields.