Name: 824-75-9|4-Fluorobenzamide|98%
Brand: Ambeed
SKU: A778029
Price: 5.0 USD
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1
[ 824-75-9 ]
[ 2757-23-5 ]
[ 52059-65-1 ]

Yield	Reaction Conditions	Operation in experiment
56%	In toluene; at 60℃;	To a stirred suspension of <strong>[824-75-9]4-fluorobenzamide</strong> (70.00 g, 503.1 mmol) in toluene (900 mL) was added chlorocarbonyl sulfenyl chloride (83.0 mL, 1.00 mol). The mixture was heated overnight at 60 C and concentrated. The resulting tan solid was triturated with methylene chloride (200 mL), collected by suction filtration and rinsed with additional methylene chloride (4 x 70 mL). The crude product was impregnated onto silica (100 g) and chromatographed in a large filter funnel dry loaded with silica using a hexane/ethyl acetate gradient. The product 5-(4-fluorophenyl)-l,3,4-oxathiazol-2-one was afforded as an off-white solid (55.98 g, 56%).
56%	In toluene; at 60℃;	To a stirred suspension of <strong>[824-75-9]4-fluorobenzamide</strong> (70.00 g, 503.1 mmol) in toluene (900 mL) was added chlorocarbonyl sulfenyl chloride (83.0 mL, 1.00 mol). The mixture was heated overnight at 60 C. and concentrated. The resulting tan solid was triturated with methylene chloride (200 mL), collected by suction filtration and rinsed with additional methylene chloride (4×70 mL). The crude product was impregnated onto silica (100 g) and chromatographed in a large filter funnel dry loaded with silica using a hexane/ethyl acetate gradient. The product 5(4-fluorophenyl)-1,3,4-oxathiazol-2-one was afforded as an off-white solid (55.98 g, 56%

Reference： [1]Journal of the Chemical Society. Perkin transactions I,1991,p. 183 - 187
[2]Patent: WO2015/89067,2015,A1 .Location in patent: Page/Page column 129; 130
[3]Patent: US9126993,2015,B2 .Location in patent: Page/Page column 54
[4]Acta Chemica Scandinavica (1947),1973,vol. 27,p. 2161 - 2170
[5]Magnetic Resonance in Chemistry,2007,vol. 45,p. 985 - 988

2
[ 824-75-9 ]
[ 1194-02-1 ]

Yield	Reaction Conditions	Operation in experiment
92%	With Triethoxysilane; [(2,5-F2C6H2-CH=N-C10H6)Co(III)(H)(PMe3)2]; In tetrahydrofuran; at 60℃; for 24h;Schlenk technique;	General procedure: To a 25 mL Schlenk tube containing a solution of 2 in 2 mL of THF was added amide (1.0 mmol) and (EtO)3SiH (0.50 g, 3.0 mmol). The reaction mixture was stirred at 60 C until there was no amide left (monitored by TLC and GC-MS). The product was purified according to literature procedures by Beller

Reference： [1]Catalysis Letters,2011,vol. 141,p. 1079 - 1085
[2]Chemistry - A European Journal,2011,vol. 17,p. 9316 - 9319
[3]European Journal of Organic Chemistry,2011,p. 4760 - 4763
[4]Chemistry - An Asian Journal,2012,vol. 7,p. 169 - 175
[5]Catalysis Communications,2019,vol. 120,p. 72 - 75
[6]Organometallics,2020
[7]Dalton Transactions,2019,vol. 48,p. 10962 - 10970
[8]Journal of Organic Chemistry,2019
[9]Journal of Organic Chemistry,2019,vol. 84,p. 6084 - 6093
[10]Applied Organometallic Chemistry,2020,vol. 34
[11]Indian Journal of Chemistry - Section B Organic and Medicinal Chemistry,1993,vol. 32,p. 385 - 386
[12]Dalton Transactions,2017,vol. 46,p. 13065 - 13076
[13]Tetrahedron Letters,1993,vol. 34,p. 1581 - 1584
[14]New Journal of Chemistry,2003,vol. 27,p. 409 - 413
[15]Catalysis Letters,2011,vol. 141,p. 1079 - 1085

3
[ 403-43-0 ]
[ 824-75-9 ]

Yield	Reaction Conditions	Operation in experiment
81%	With ammonium hydroxide In water; ethyl acetate at 0℃; for 0.5h;
	With ammonium hydroxide In ethyl acetate for 0.166667h;
	With ammonium hydroxide In tetrahydrofuran; water at 0℃; for 1h; Inert atmosphere;

	With ammonium hydroxide In tetrahydrofuran at 20℃; for 2h;	General procedure for the synthesis of amides (1a-n) General procedure: To a solution of an appropriate substituted carboxylic acid (10 mmol) in CHCl3 (50 mL) was added thionyl chloride (3.6 mL, 50 mmol), dropwise over 10 min. The resulting solution was refluxed for 8 h and then concentrated in vacuo. The residual light brown oil was dissolved in THF (50 mL), diluted with a solution of 30% NH4OH (6 mL), and stirred at room temperature for an additional 2 h. At that point, saturated aqueous NaHCO3 (10 mL) was added and the reaction mixture was extracted with EtOAc (3 × 30 mL). The combined organic layer was washed with brine (50 mL), dried over anhydrous Na2SO4, and concentrated in vacuo. The crude amide was carried directly to the next step without further purification.
590 mg	With ammonium hydroxide In dichloromethane; water at 20℃; for 4h;
	With ammonium hydroxide at 0℃;
	With ammonium hydroxide In dichloromethane for 0.5h; Cooling with ice;
	With ammonium hydroxide at 0 - 10℃; for 1h;	General synthetic procedure for compounds 3a-3t General procedure: A solution of thionyl chloride (25 mmol) was addeddropwisely to 1 (20 mmol) in toluene(15 mL). The mixture was heated to reflux for 3 h. Excess thionyl chloride wasremoved in vacuo. The remained mixture was added dropwise to ammonia waterbelow 10 °C, then stirred at 10 °C for 1 h. The intermediate 3 was obtained as white solid by filtration.
	With ammonium hydroxide In dichloromethane; water at 20℃; for 4h;	4b Figure 1 shows the reaction scheme for the synthesis of Compound of compound 4 (A): SOCI2, Et3N, NH4OH, CH2CI2 (B): 1 3-dichloroacetone; (C): Na2CO3, DMF.Compounds 4a,b were synthesized as described in Figure 1. Synthesis of compounds2a-4a has been reported previously, and spectral data of these compounds were identical to those previously described in MedChem, vol. 4, no. 2, pp. 188-95, Feb. 2009. 4-Fluorobenzamide (2b) was prepared from the corresponding commercially available 4-fluorobenzoic acid (1 b, 1 mmol), which was treated with an excess of 50C12(7 mmol) in presence of Et3N (0.1 mmol) under reflux for 1 h. The resulting acyl chloride was added to a mixture (45 mL) of NH4OH (28 %), H20 and CH2CI2 (1:1:1 vlvlv). The mixture was stirred at room temperature for 4 h. The organic layer was separated from the aqueous layer and washed with 2 M NaOH (3 x 10 mL). The organic solution was dried over Na2504 and evaporated. The residue was purified by silica gel columnchromatography (CH2CI2/MeOH 95:5 vlv). The yield of brown solid 2b was 30 %. GC- MS m/z: 139 (M, 67), 123 (100), 95 (72).
	Multi-step reaction with 2 steps 1.1: toluene / 12 h / 20 °C / Inert atmosphere; Sealed tube; Darkness 1.2: 14 h / 20 °C / Inert atmosphere 2.1: ammonia; 1,8-diazabicyclo[5.4.0]undec-7-ene / dimethyl sulfoxide; toluene / 1 h / 80 °C / 750 Torr / Inert atmosphere
	Multi-step reaction with 2 steps 1: sodium hydroxide / Cooling with ice 2: copper dichloride / dimethyl sulfoxide / 11 h / 120 °C
	Multi-step reaction with 2 steps 1: sodium hydroxide 2: copper dichloride / dimethyl sulfoxide / 11 h / 120 °C
	With ammonium chloride; triethylamine; 1,1'-carbonyldiimidazole In dichloromethane at 25℃; for 1h;	General procedure for synthesis of primary amides General procedure: The 50 mL two necked round bottom with magnetic bar and septum was charged with benzoyl chloride (1.0 g, 7.11 mmol, 1.0 eq) and 1,1'-carbonyldiimidazole (1.27 g, 7.83 mmol, 1.1 eq) and methylene chloride (MC, 21.3 mL). To this, NEt3 (2.50 ml, 17.78 mmol, 2.5 eq) and ammonium chloride (0.5708 g, 10.67 mmol, 1.5 eq) were added at 25 °C, stirred for 1 h. After completion of reaction (monitored by TLC), crude mixture was extracted with MC, washed with water and brine solution. The organic part was dried over MgSO4, filtered and dried under reduced pressure. Crude compound was purified by silica gel chromatography.

Reference： [1]Louvel, Julien; Guo, Dong; Agliardi, Marta; Mocking, Tamara A. M.; Kars, Roland; Pham, Tan Phát; Xia, Lizi; De Vries, Henk; Brussee, Johannes; Heitman, Laura H.; Ijzerman, Adriaan P. [Journal of Medicinal Chemistry, 2014, vol. 57, # 8, p. 3213 - 3222]
[2]Weikert; Bingham Jr.; Emanuel; Fraser-Smith; Loughhead; Nelson; Poulton [Journal of Medicinal Chemistry, 1991, vol. 34, # 5, p. 1630 - 1633]
[3]Location in patent: experimental part Prediger, Patricia; Barbosa, Lais Ferreira; Genisson, Yves; Correia, Carlos Roque Duarte [Journal of Organic Chemistry, 2011, vol. 76, # 19, p. 7737 - 7749]
[4]Yang, Jianzhong; Pi, Weiyi; Xiong, Li; Ang, Wei; Yang, Tao; He, Jun; Liu, Yuanyuan; Chang, Ying; Ye, Weiwei; Wang, Zhenling; Luo, Youfu; Wei, Yuquan [Bioorganic and Medicinal Chemistry Letters, 2013, vol. 23, # 5, p. 1424 - 1427]
[5]Savolainen, Heli; Cantore, Mariangela; Colabufo, Nicola A.; Elsinga, Philip H.; Windhorst, Albert D.; Luurtsema, Gert [Molecular Pharmaceutics, 2015, vol. 12, # 7, p. 2265 - 2275]
[6]Wang, Sen-Lin; Shi, Yu-Jun; He, Hai-Bing; Li, Yu; Li, Yang; Dai, Hong [Chinese Chemical Letters, 2015, vol. 26, # 6, p. 672 - 674]
[7]Wu, Youzhi; Sun, Peng; Zhang, Kaifan; Yang, Tie; Yao, Hequan; Lin, Aijun [Journal of Organic Chemistry, 2016, vol. 81, # 5, p. 2166 - 2173]
[8]Lei, Peng; Xu, Yan; Du, Juan; Yang, Xin-Ling; Yuan, Hui-Zhu; Xu, Gao-Fei; Ling, Yun [Bioorganic and Medicinal Chemistry Letters, 2016, vol. 26, # 10, p. 2544 - 2546]
[9]Current Patent Assignee: BIOFORDRUG SRL; NETHERLANDS ORGANISATION FOR SCIENTIFIC RESEARCH; VU UNIVERSITY MEDICAL CENTRE AMSTERDAM; UNIVERSITY MEDICAL CENTER GRONINGEN; UNIVERSITY OF GRONINGEN - WO2015/194954, 2015, A1 Location in patent: Page/Page column 8
[10]Wang, Justin Y.; Strom, Alexandra E.; Hartwig, John F. [Journal of the American Chemical Society, 2018, vol. 140, # 25, p. 7979 - 7993]
[11]Chen, Junmin; Liu, Wei; Zhao, Yongli; Zhou, Liandi [ARKIVOC, 2016, vol. 2016, # 6, p. 52 - 62]
[12]Zhou, Liandi; Liu, Wei; Zhao, Yongli; Chen, Junmin [Arkivoc, 2021, vol. 2016, # 6, p. 52 - 62]
[13]Yi, Jaeeun; Kim, Hyun Tae; Jaladi, Ashok Kumar; An, Duk Keun [Bulletin of the Korean Chemical Society, 2022, vol. 43, # 1, p. 129 - 132]

4
[ 120-72-9 ]
[ 824-75-9 ]
4-(1H-indol-1-yl)benzamide [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
88%	With potassium fluoride on basic alumina In dimethyl sulfoxide at 120℃;
45%	With aluminum oxide; potassium fluoride; 18-crown-6 ether In dimethyl sulfoxide at 180℃; for 2h; Microwave irradiation; Inert atmosphere;

Reference： [1]Smith III, William J.; Sawyer, J. Scott [Tetrahedron Letters, 1996, vol. 37, # 3, p. 299 - 302]
[2]Location in patent: scheme or table Frayne, Gregory L.; Green, Gary M. [Tetrahedron Letters, 2008, vol. 49, # 51, p. 7328 - 7329]

5
[ 824-75-9 ]
[ 534-07-6 ]
[ 22091-39-0 ]

Yield	Reaction Conditions	Operation in experiment
64%	With sulfuric acid;	Method 2 4-Chloromethyl-2-(4-fluorophenyl)oxazole 139 g (1 mol) of <strong>[824-75-9]4-fluorobenzamide</strong> and 127 g (1 mol) of 1,3-dichloroacetone are combined in a reaction vessel with a connected scrubbing tower. The mixture is melted slowly by heating, and the temperature is finally increased to 150 C. This temperature is maintained while stirring until evolution of gas is complete (about 1.5 hours). The dark reaction mixture is cooled to room temperature, 500 ml of concentrated sulfuric acid are carefully added dropwise and the resulting suspension is stirred for 1.5 hours. The mixture is then poured into ice water while stirring vigorously, and the precipitate is filtered off under suction and washed thoroughly with water. The precipitate is dried and then recrystallized from ethanol. Yield: 64%; melting point: 71-74 C.
32%		EXAMPLE 24-(Chloromethyl)-2-(4-fluorophenyl)oxazoleA mixture of <strong>[824-75-9]4-fluorobenzamide</strong> (2.5 g, 17.9 mmol) and 1 ,3-dichloroacetone (2.7 g, 21 .6 mmol) in EtOH-THF (20 mL-10 ml.) was heated to 85 C for 24 h. The reaction mixture was cooled to room temperature and quenched with 10% NaHC03 solution. The organic product was extracted with EtOAc and the organic layer was washed with H20 and brine, dried over anhydrous sodium sulfate and concentrated under reduced pressure. The crude product was purified by column chromatography (silica gel 60-120 mesh, eluent 6-10% EtOAc in petroleum ether) to afford 4-(chloromethyl)-2-(4- fluorophenyl)oxazole (1 .2 g, yield 32%) as white solid. 1 H NMR (300MHz, CDCI3) delta 8.07 - 8.02 (m, 2H), 7.70 (m, 1 H), 7.19 - 7.13 (t, J = 8.8 Hz, 2H), 4.58 (m, 2H). MS (ESI) m/z: Calculated for C10H7FCINO: 21 1.02; found: 212.0 (M+H)+
32%	In tetrahydrofuran; ethanol; at 85℃; for 24h;	A mixture of <strong>[824-75-9]4-fluorobenzamide</strong> (2.5 g, 17.9 mmol) and 1,3-dichloroacetone (2.7 g, 21.6 mmol) in EtOH-THF (20 mL-10 mL) was heated to 85 C for 24 h. The reaction mixture was cooled to room temperature and quenched with 10% NaHCO3 solution. The organic product was extracted with EtOAc and the organic layer was washed with H2O and brine, dried over anhydrous sodium sulfate and concentrated under reduced pressure. The crude product was purified by column chromatography (silica gel 60-120 mesh, eluent 6-10% EtOAc in petroleum ether) to afford 4-(chloromethyl)-2-(4-fluorophenyl)oxazole (1.2 g, yield 32%) as a white solid. 1H NMR (300MHz, CDCl3) delta 8.07 - 8.02 (m, 2H), 7.70 (m, 1 H), 7.19-7.13 (t, J = 8.8 Hz, 2H), 4.58 (m, 2H). MS (ESI) m/z: Calculated for C10H7FClNO: 211.02; found: 212.0 (M+H)+.

30%	at 200℃; for 5h;	4-(Chloromethyl)-2-(4-fluorophenyl)oxazole (3b) was prepared condensing amide2b with 1,3-dichloroacetone (2 mmol) while heating at 200 C for 5 h. After cooling to room temperature, water (10 mL) and CHCI3 (10 mL) were added. The aqueous phasewas extracted with CHCI3 (3 x 50 mL), and the combined organic layers were dried overNa2504 and evaporated. The residue was purified on silica gel column chromatography(EtPt/AcOEt 8:2 v/v) yielding 30 % of 3b as a brown solid. GC-MS m/z: 213 (M+2, 19),211 (M, 57), 176 (78). 1H NMR (CDCI3) O: 4.32 (5, 2H, CH2), 7.12-7.16 (m, 2H), 7.6 (5,1H), 8.03 (dd, 2H, J= 1.9, 8.1 Hz).
	In n-heptane; ethyl acetate;	EXAMPLE II At 120 C., 31 g (123 mmol) of <strong>[824-75-9]p-fluorobenzamide</strong> and 33 g (123 mmol) of 1,3-dichloroacetone were stirred in the absence of a solvent for 2 hours. After cooling to room temperature, the product was dissolved in 250 ml of ethyl acetate. This solution was diluted with 400 ml of n-heptane and washed 3 times with saturated NaCl solution. The organic phase was filtered through 250 ml of silica gel, and the filter pad was then washed with 200 ml of n-heptane/ethyl acetate (4:1). The solvent was distilled off, giving 4-chloromethyl-2-(4-fluorophenyl)oxazole 1 as crude product. This was dissolved in 650 ml of acetone, and 90 g of NaI were then added. The mixture was then heated at reflux for 16 hours, most of the solvent was then removed and the solid residue was suspended in 200 ml of n-heptane/ethyl acetate (1:1) and filtered through 200 ml of silica gel. The precipitate was washed with 500 ml of n-heptane/ethyl acetate (1:1), and the organic phase was concentrated. On concentration, the iodide 2 began to crystallize as white crystals. TLC n-heptane/ethyl acetate (6:1) Rf=0.4 for 2 and Rf=0.35 for 1. C10H7FINO (303.08) MS(ESI): 304 (M+H+).
	at 120℃; for 2h;	At 120 C., 31 g (123 mmol) of <strong>[824-75-9]p-fluorobenzamide</strong> and 33 g (123 mmol) of 1,3-dichloroacetone were stirred in the absence of a solvent for 2 hours.After cooling to room temperature, the product was dissolved in 250 ml of ethyl acetate.This solution was diluted with 400 ml of n-heptane and washed 3 times with saturated NaCl solution.The organic phase was filtered through 250 ml of silica gel, and the filter pad was then washed with 200 ml of n-heptane/ethyl acetate (4:1).The solvent was distilled off, giving 4-chloromethyl-2-(4-fluorophenyl)oxazole 1 as crude product.This was dissolved in 650 ml of acetone, and 90 g of NaI were then added.The mixture was then heated at reflux for 16 hours, most of the solvent was then removed and the solid residue was suspended in 200 ml of n-heptane/ethyl acetate (1:1) and filtered through 200 ml of silica gel.The precipitate was washed with 500 ml of n-heptane/ethyl acetate (1:1), and the organic phase was concentrated.On concentration, the iodide 2 began to crystallize as white crystals. TLC n-heptane/ethyl acetate (6:1) Rf=0.4 for 2 and Rf=0.35 for 1. C10H7FINO (303.08) MS(ESI): 304 (M+H+).

Reference： [1]Journal of Medicinal Chemistry,2014,vol. 57,p. 3213 - 3222
[2]Patent: US5489605,1996,A
[3]Patent: WO2011/88187,2011,A1 .Location in patent: Page/Page column 39-40
[4]Patent: EP2533783,2015,B1 .Location in patent: Paragraph 0601-0602
[5]Molecular Pharmaceutics,2015,vol. 12,p. 2265 - 2275
[6]Patent: WO2015/194954,2015,A1 .Location in patent: Page/Page column 8
[7]Journal of Medicinal Chemistry,1996,vol. 39,p. 237 - 245
[8]Patent: US2005/267177,2005,A1
[9]Patent: US2004/122069,2004,A1 .Location in patent: Page 14
[10]Bioorganic and Medicinal Chemistry Letters,2010,vol. 20,p. 2933 - 2937
[11]Chinese Chemical Letters,2015,vol. 26,p. 672 - 674

6
[ 824-75-9 ]
[ 100-52-7 ]
[ 725-38-2 ]

Yield	Reaction Conditions	Operation in experiment
93%	With triethylsilane; trifluoroacetic acid In toluene at 120℃; for 18h;
88%	With L-Tartaric acid; hydrogen In toluene at 135℃; for 24h; Autoclave;	4.3. General procedure for reductive N-alkylation of amides General procedure: The magnetic stirring bar, 0.5 mmol of amide and 0.5 mmol ofaldehyde were transferred to 8 mL glass vial and then 3 mL solvent(Toluene) was added. Then, 60 mg of catalyst (Ni-TA-MISiO2-800;11 mol% Ni) was added and the vial was fitted with septum, cap andneedle. The reaction vials (8 vials with different substrates at atime) were placed into a 300 mL autoclave. The autoclave wasflushed with hydrogen twice at 20 bar pressure and then it waspressurized with 50 bar hydrogen. The autoclavewas placed into analuminum block preheated at 145 C (placed 30 min beforecounting the reaction time in ordered to attain reaction temperature)and the reactions were stirred for required time. During thereaction the inside temperature of the autoclave was measured to be 135 C and this temperature was used as the reaction temperature.After the completion of the reactions, the autoclave wascooled to room temperature. The remaining hydrogen was dischargedand the vials containing reaction products were removedfrom the autoclave. The solid catalyst was filtered off and washedthoroughly with ethyl acetate. The reaction products were analyzedby GC-MS. The corresponding crude product was purified by flashcolumn chromatography and characterized by NMR and GC-MSanalysis. The yields were determined by GC for the selected compounds:After completion of the reaction, n-hexadecane (100 mL) asstandard was added to the reaction vials and the reaction productswere diluted with ethyl acetate followed by filtration using plug ofsilica and then analyzed by GC.

Reference： [1]Dube, Daniel; Scholte, Andrew A. [Tetrahedron Letters, 1999, vol. 40, # 12, p. 2295 - 2298]
[2]Alenad, Asma M.; Alshammari, Ahmad S.; Jagadeesh, Rajenahally V.; Murugesan, Kathiravan; Sohail, Manzar [Tetrahedron, 2021, vol. 102]

7
[ 1194-02-1 ]
[ 824-75-9 ]

Yield	Reaction Conditions	Operation in experiment
96%	With water; at 140℃; for 6h;Sealed tube;	General procedure: In a typical reaction procedure 1 mmol benzonitrile and3 ml of H2O was taken in a sealed tube. About 80 mg ofcatalyst was added to this reaction mixture and stirred at140 C on a oil bath for stipulated reaction time. Theprogress of the reaction was monitored by using thin layerchromatography. The products were identified by GC-MS(SHIMADZU-2010) analysis by separating the products ona DB-5 column.
94%	With 1,3-bis(2,4,6-trimethylphenyl)imidazole-2-ylidene silver chloride; water; at 50℃; for 7.5h;	General procedure: Synthesis of benzamide (2a) : (0.03 mmol) of Ag(I)-NHC catalyst (3a) was added to 1 mL of H2O in 5 mL round bottom flask. To this 1 mmol of benzonitrile (1a) was added and the reaction mixture was stirred for 8 h at 50 C. After the completion of reaction as monitored by TLC, the resulting mixture was filtered through a pad of celite and extracted with DCM (2 x 5 mL). The combined organic phase was concentrated under reduced pressure. The crude product was purified by column chromatography using a gradient of hexane/ethyl acetate (1:1). The compound 2a (91%) was isolated as a white solid. Similar procedure was followed to synthesize other amides 2b-2x.

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[50]Patent: CN111153825,2020,A .Location in patent: Paragraph 0128; 0129
[51]Patent: CN111153824,2020,A .Location in patent: Paragraph 0118-0119

8
[ 824-75-9 ]
[ 22179-72-2 ]

Yield	Reaction Conditions	Operation in experiment
	With Lawessons reagent In toluene Heating;
	With Lawessons reagent In tetrahydrofuran at 23℃; for 1h;	4.2. Preparation of thioamides 2. General procedure General procedure: Amides (1 mmol) and Lawesson's reagent (490 mg, 1.2 mmol) were added to dry THF (15 mL). The reaction mixture was stirred at room temperature for 1 h, or heated under reflux for 5 h in the case of the 4-nitro derivative. The solvent was evaporated under reduced pressure and the residue was partitioned between aq NaHCO3 (25 mL) and ethyl acetate (25 mL). The organic solvent was separated and dried over anhydrous MgSO4. The crude product was further purified by silica gel flash chromatography, using hexane-ethyl acetate (4:1), to yield the corresponding thioamides as yellow solids (42-60%). 4-Nitrothioamide (2ff),38 4-cyanothiobenzamide (2gg)39 and 3-cyanothiobenzamide (2hh),40 3-methoxythiobenzamide (2ii)41 have been previously reported.
	With Lawessons reagent In benzene for 0.25h; Reflux;

	With Lawessons reagent In tetrahydrofuran Reflux;	General procedure for the synthesis of thioamides (2a-n) General procedure: The mixture of the corresponding amide (0.2 mmol) and Lawesson’s reagent (0.3 mmol) in tetrahydrofuran 4 mL was refluxed and the reaction was monitored by thin layer chromatography (TLC). After the reaction was complete, the crude product was puried by silica-gel column chromatography using ethyl acetate/hexane as eluent solvent system. The pure product was obtained and identified.
	Multi-step reaction with 2 steps 1: water / 90 °C / Green chemistry 2: water / 90 °C / Green chemistry
	With Lawessons reagent
	With Lawessons reagent In tetrahydrofuran for 4h; Reflux;	General synthetic procedure forintermediates 13a-u General procedure: To a solution of benzamide 11a-u (1 equiv) in THF (30mL) was added Lawesson’s reagent (0.6 equiv), and the mixture was heated to reflux for 4 hrs. The reaction mixture was concentrated invacuo,then diluted with ethyl acetate (30 ml), and washed with 1N NaHCO3 (3× 20 mL) and brine (2 × 20 mL). The organic layer was dried over anhydrous sodium sulfate,filtered and evaporated under reduced pressure. The crude product was purified by silica gel column chromatography using a mixture of dichloromethane/methanol(100:1, v/v) as eluent to afford a yellow solid product.A solution of the obtained solid 12a-u (1 equiv) and ethyl 2-chloroacetoacetate (1.2 equiv) in ethanol (25 ml) was heated to reflux for 6 h, then the mixture was allowed to stand at 0 °C for 10 hrs, and a white needle crystal was precipitate out.The reaction mixture was filtered and the filter cake was washed with 10 mL of ethanol, dried in vacuum to give the desired product.
	With Lawessons reagent In toluene at 115℃; for 0.5h;
	With Lawessons reagent In tetrahydrofuran at 65℃; for 3h;

Reference： [1]Bongartz, Jean-Pierre; Stokbroekx, Raymond; Van der Aa, Marcel; Luyckx, Marcel; Willems, Marc; Ceusters, Marc; Meerpoel, Lieven; Smets, Gerda; Jansen, Tine; Wouters, Walter; Bowden, Charlie; Valletta, Lisa; Herb, Mark; Tominovich, Rose; Tuman, Robert [Bioorganic and Medicinal Chemistry Letters, 2002, vol. 12, # 4, p. 589 - 591]
[2]Location in patent: experimental part Mayhoub, Abdelrahman S.; Marler, Laura; Kondratyuk, Tamara P.; Park, Eun-Jung; Pezzuto, John M.; Cushman, Mark [Bioorganic and Medicinal Chemistry, 2012, vol. 20, # 1, p. 510 - 520]
[3]Location in patent: experimental part Diana, Patrizia; Carbone, Anna; Barraja, Paola; Montalbano, Alessandra; Parrino, Barbara; Lopergolo, Alessia; Pennati, Marzia; Zaffaroni, Nadia; Cirrincione, Girolamo [ChemMedChem, 2011, vol. 6, # 7, p. 1300 - 1309]
[4]Yang, Jianzhong; Pi, Weiyi; Xiong, Li; Ang, Wei; Yang, Tao; He, Jun; Liu, Yuanyuan; Chang, Ying; Ye, Weiwei; Wang, Zhenling; Luo, Youfu; Wei, Yuquan [Bioorganic and Medicinal Chemistry Letters, 2013, vol. 23, # 5, p. 1424 - 1427]
[5]Yadav, Arvind K.; Srivastava, Vishnu P.; Yadav, Lal Dhar S. [Synthetic Communications, 2014, vol. 44, # 3, p. 408 - 416]
[6]Eccles, Kevin S.; Morrison, Robin E.; Maguire, Anita R.; Lawrence, Simon E. [Crystal Growth and Design, 2014, vol. 14, # 6, p. 2753 - 2762]
[7]Li, Zheng; Qiu, Qianqian; Xu, Xue; Wang, Xuekun; Jiao, Lei; Su, Xin; Pan, Miaobo; Huang, Wenlong; Qian, Hai [European Journal of Medicinal Chemistry, 2016, vol. 113, p. 246 - 257]
[8]Peng, Xiangjun; Qin, Feng; Xu, Mengyue; Zhu, Shaojie; Pan, Yingming; Tang, Haitao; Meng, Xiujin; Wang, Hengshan [Organic and Biomolecular Chemistry, 2019, vol. 17, # 36, p. 8403 - 8407]
[9]Chiarelli, Laurent R.; Fan, Dongguang; Han, Quanquan; Lu, Yu; Qiao, Chunhua; Shi, Rui; Stelitano, Giovanni; Wang, Bin; Huszár, Stanislav; Mikušová, Katarína; Savková, Karin [Journal of Medicinal Chemistry, 2021, vol. 64, # 19, p. 14526 - 14539]

9
[ 459-57-4 ]
[ 824-75-9 ]

Yield	Reaction Conditions	Operation in experiment
91%	With hydroxylamine hydrochloride; sodium carbonate; scandium tris(trifluoromethanesulfonate); In water; at 135℃; for 0.45h;Microwave irradiation; Sealed vial;	General MW procedure: A mixture of Sc(OTf)3 (10 mol %, 49 mg), aldehyde (1 mmol), NH2OH·HCl (1 mmol, 69 mg) and Na2CO3 (1 mmol) was placed in a safe pressure regulation 10 mL pressurized vial containing H2O (1 mL). The vial was sealed with a ?snap-on? cap and irradiated in a single-mode CEM Discover Bench Mate microwave reactor at 300 W and 135 C for 15-35 min. After the reaction was complete (periodic TLC monitoring), the mixture was allowed to cool to room temperature and was extracted with EtOAc (3 × 10 mL). The combined organic phase was dried over Na2SO4, filtered and the solvent was removed under vacuum. The leftover residue was purified by column chromatography on silica gel (EtOAc/hexane 3:7 as eluent) and then characterized based on their physical and spectral data.
90%	With hydroxylamine hydrochloride; potassium carbonate; In dimethyl sulfoxide; at 120℃; for 48h;Green chemistry;	General procedure: In a typical method, benzaldehyde (1.0 mmol), hydroxylaminehydrochloride (1.5 mmol), potassium carbonate (2.5 mmol) and0.5 mL of as-prepared SEF127-Pd(nanoparticle)/GO in DMSO were added to reaction media in the presence of 1.5 mL DMSO. The reac-tion was allowed to stir at 120C. Upon reaction completion, thecatalyst was separated by centrifuge and the organic residue was extracted with dichloromethane and evaporated under reducedpressure. The organic residue was purified by column chromatography. All yields were reported based on isolated amount. All productsare known and identified by 1H-NMR,13C-NMR spectrum and physical properties.
89%	With C17H17BrClN2RuSe(1+)*F6P(1-); hydroxylamine hydrochloride; sodium hydroxide; In toluene; at 100℃; for 12h;	General procedure: In an oven-dried 100mL two-neck round bottom flask, amixture of aryl-aldehyde (1.0 mmol), NH2OH.HCl (1.0 mmol), NaOH (1.0 mmol), catalyst (0.1 mol%) and solvent (5 ml) were heated at 100 C with continuous stirring for 12 h in air. The progress of the reaction was continuously monitored by TLC until the maximum conversion of an aldehyde to the desired product observed. After completion, the reaction mixture was cooled to room temperature and extracted in ethyl acetate (2 25 mL). This extract was further washed with water and dried over anhydrous Na2SO4. The product was purified by column chromatography after removing the solventon a rotary evaporator under reduced pressure. All the desired product obtained as white solid was authenticated by HR-MS, 1H,and 13C{1H} NMR spectroscopy.

60%

With tert.-butylhydroperoxide; copper nanoparticles on black carbon; sodium carbonate; ammonium chloride; In acetonitrile; at 60℃; for 6h;Inert atmosphere;

General procedure: To a mixture of catalyst (20 mg, 3.68 mol %), amine hydrochloride salt (2 mmol) and Na2CO3 (212 mg, 2 mmol) in acetonitrile (1 mL) was added aldehyde (1 mmol) and TBHP (1.5 equiv) under an argon atmosphere at room temperature. The reaction vessel was capped and stirred at 60 C for 6 h. The progress of the reaction was monitored by thin-layer chromatography. After completion, the reaction mixture was allowed to cool to room temperature, then diluted with ethyl acetate and the catalyst separated from the reaction mixture by filtration. The combined organic layers were concentrated under vacuum and the resulting residue was purified by column chromatography.

Reference： [1]Catalysis science and technology,2015,vol. 5,p. 199 - 205
[2]European Journal of Organic Chemistry,2014,vol. 2014,p. 7590 - 7593
[3]Tetrahedron Letters,2011,vol. 52,p. 5851 - 5854
[4]Journal of Molecular Catalysis A: Chemical,2016,vol. 416,p. 88 - 95
[5]Journal of Organometallic Chemistry,2019,vol. 879,p. 69 - 77
[6]Applied Organometallic Chemistry,2018,vol. 32
[7]Dalton Transactions,2014,vol. 43,p. 12365 - 12372
[8]RSC Advances,2016,vol. 6,p. 37093 - 37098
[9]Journal of Chemical Research,2012,vol. 36,p. 460 - 462
[10]Organic and Biomolecular Chemistry,2014,vol. 12,p. 414 - 417
[11]Organic Letters,2016,vol. 18,p. 5788 - 5791
[12]Advanced Synthesis and Catalysis,2010,vol. 352,p. 288 - 292
[13]RSC Advances,2015,vol. 5,p. 44524 - 44529
[14]Journal of Organic Chemistry,2019,vol. 84,p. 8468 - 8480
[15]Catalysis Communications,2017,vol. 91,p. 38 - 42
[16]Green Chemistry,2018,vol. 20,p. 266 - 273
[17]Applied Organometallic Chemistry,2014,vol. 28,p. 101 - 108
[18]Tetrahedron Letters,2016,vol. 57,p. 95 - 99
[19]Journal of Organic Chemistry,2012,vol. 77,p. 8007 - 8015,9
[20]Organic Letters,2007,vol. 9,p. 73 - 75
[21]Organometallics,2012,vol. 31,p. 6482 - 6490
[22]ChemCatChem,2013,vol. 5,p. 2462 - 2470

10
[ 109-09-1 ]
[ 824-75-9 ]
[ 325-97-3 ]

Yield	Reaction Conditions	Operation in experiment
89%	With potassium carbonate;palladium diacetate; 1,3-bis-(diphenylphosphino)propane; In 1,4-dioxane; at 80℃;Heating / reflux;	EXAMPLE 9Coupling of 2-chloropyridine with <strong>[824-75-9]4-fluorobenzamide</strong> (catalyst: Pd(OAc)2/2,2-dimethyl-1,3-bis(diphenylphosphino)propane)4.0 g of potassium carbonate (28.9 mmol), 3.5 g of <strong>[824-75-9]4-fluorobenzamide</strong> (25.3 mmol) and 2.1 g of 2-chloropyridine (18.1 mmol) are dissolved or suspended in 25 ml of dioxane and admixed at 80 C. with a suspension of 0.036 g of palladium(II) acetate (0.9 mol %) and 0.200 g of 1,3-bis(diphenylphosphino)propane (2.5 mol %). The mixture is subsequently refluxed and the conversion is monitored by HPLC. After boiling overnight, the conversion is >98%. The work-up is carried out by addition of water to dissolve the precipitated salts, addition of toluene and phase separation. The upper, product-containing phase is evaporated on a rotary evaporator and the product is purified by chromatography. This gave 3.5 g (89%) of coupling product (4-fluoro-N-pyridin-2-yl-benzamide).

Reference： [1]Patent: US2008/39633,2008,A1 .Location in patent: Page/Page column 5

11
[ 459-56-3 ]
[ 824-75-9 ]

Yield	Reaction Conditions	Operation in experiment
99%	With ammonium hydroxide; manganese(IV) oxide; oxygen at 130℃; for 24h; Autoclave;	2.2. Catalytic evaluation General procedure: The ammoxidation of alcohols and hydration of nitrileswere performed in a high-pressure steel autoclave reactorequipped with a PTFE bottle, magnetic stirrer (900 rpm), andan explosion-proof pressure sensor. For the ammoxidation ofalcohols, the as-prepared catalyst, aqueous ammonia(28%-30% NH3), and alcohols were added into a certainamount of t-amyl alcohol solvent in the reactor, then the autoclavewas sealed and purged with oxygen for two times to excludethe inside air. For the hydration of nitrile, the as-preparedcatalyst, nitrile, and water were added into a certain amount oft-amyl alcohol solvent in the reactor, then the autoclave wassealed and purged with N2 for two times to exclude the insideair. After that, the reactor was quickly heated to the desiredtemperature (the reaction temperature was measured by athermocouple in the autoclave) in an oil bath. After a desiredreaction time, the reactor was placed in an ice bath to quenchthe reaction. After separation of the solid catalyst by centrifugation,the liquid was analyzed with a Shimadzu GC-2014 gaschromatograph equipped with a flame ionization detector(FID) and an Agilent HP-6890 gas chromatograph-mass spectrometer,with ethylbenzene, bromobenzene, hexadecane, orbiphenyl used as internal standards. The gas-phase products,such as CO and CO2, were analyzed with a Fu Li-9790 gaschromatograph equipped with a thermal conductivity detector(TCD). Notably, no CO and CO2 signals were observed in TCDand total carbon balances were always >90.0% in this work.Safety Note: The high-pressure oxygen has been extensivelyused in the aerobic oxidations [21,22], and the reaction systemsin this work were out of the explosion limits of the reactants.For example, the explosion limit of benzyl alcohol is1.3%-13.0% in oxygen, and the concentration of benzyl alcoholin the gaseous phase in this work is in a 0-0.4% region, whichis out of the explosion limits. Furthermore, the fire and staticelectricity are not allowed to access the internal reactor forsafety reasons. In the kinetics study, the average reaction rateswere calculated from the moles of substrate converted pergram of catalyst in one hour (mmol gcat-1 h-1), with the conversionof substrate controlled to be lower than 20.0%.
98%	With tert.-butylhydroperoxide; ammonia; oxygen In water; N,N-dimethyl-formamide at 80℃; for 5h; Green chemistry;
96%	With ammonium hydroxide In water at 120℃; for 24h; Sealed tube; Autoclave;	S8. Procedure for the synthesis of amides General procedure: A magnetic stir bar and the alcohol substrate were transferred to 8 mL glass vial and then 2 mL of H2O wasadded. Then, 3 mg catalyst was added followed by the addition of aq. NH3. Then, the vial was f itted with aseptum, cap, and needle. The reaction vials were placed into a 300 mL autoclave (8 vials containing differentsubstrates were placed at a time in the autoclave) and then the autoclave was pressurized with 10 bar air. Theautoclave was placed into an aluminium block and the temperature of the aluminum block was set in orderobtain 120 °C inside the autoclave. Temperature of the aluminum block was set to 130 oC to attain 120 oCinside the autoclave, which was considered as the reaction temperature. The reactions were allowed toprogress under continuous stirring for the required time at 120 °C. Af ter completion of the reaction, theautoclave was cooled down to room temperature and the remaining air was gradually discharged. Afterwards,the catalyst was f iltered-off and washed with methanol. The solvent f rom the f iltrate containing the reactionproducts was removed in vacuum and the corresponding amide was purified by column chromatography. Allproducts were analyzed by GC-MS and NMR spectroscopy analysis.

92%	With hydroxylamine hydrochloride; dihydrogen peroxide; potassium carbonate In water at 80℃; for 20h;
92%	With hydroxylamine hydrochloride; dihydrogen peroxide; potassium carbonate In water at 80℃; Green chemistry;
77%	With tert.-butylhydroperoxide; tetraethylammonium iodide; ammonium bicarbonate In 1,2-dichloro-ethane at 70℃; for 22h;
72%	With tert.-butylhydroperoxide; ammonium hydroxide In water at 100℃; for 16h;
	Multi-step reaction with 2 steps 1: cesium carbonate; styrene / iridium pentamethylcyclopentadienyl dichloride dimer / toluene / 24 h / 111 °C 2: 117 mg / hydroxylamine hydrochloride / iridium pentamethylcyclopentadienyl dichloride dimer / toluene / 16 h / 111 °C
61 %Chromat.	With ammonium acetate; oxygen In tert-Amyl alcohol at 130℃; for 18h; Autoclave;

Reference： [1]Wang, Hai; Luo, Qingsong; Wang, Liang; Hui, Yu; Qin, Yucai; Song, Lijuan; Xiao, Feng-Shou [Cuihua Xuebao/Chinese Journal of Catalysis, 2021, vol. 42, # 12, p. 2164 - 2172]
[2]Molla, Rostam Ali; Ghosh, Kajari; Tuhina; Manirul Islam [New Journal of Chemistry, 2015, vol. 39, # 2, p. 921 - 930]
[3]Bartling, Stephan; Beller, Matthias; Chandrashekhar, Vishwas G.; Jagadeesh, Rajenahally V.; Rabeah, Jabor; Rockstroh, Nils; Senthamarai, Thirusangumurugan [Chem, 2022, vol. 8, # 2, p. 508 - 531]
[4]Gholipour, Behnam; Liu, Xiao; Rostamnia, Sadegh; Zonouzi, Afsaneh [RSC Advances, 2022, vol. 12, # 7, p. 4276 - 4287]
[5]Gholipour, Behnam; Liu, Xiao; Rostamnia, Sadegh; Zonouzi, Afsaneh [RSC Advances, 2022, vol. 12, # 7, p. 4276 - 4287]
[6]Wang, Gao; Yu, Qing-Ying; Chen, Shan-Yong; Yu, Xiao-Qi [Organic and Biomolecular Chemistry, 2014, vol. 12, # 3, p. 414 - 417]
[7]Wu, Xiao-Feng; Sharif, Muhammad; Feng, Jian-Bo; Neumann, Helfried; Pews-Davtyan, Anahit; Langer, Peter; Beller, Matthias [Green Chemistry, 2013, vol. 15, # 7, p. 1956 - 1961]
[8]Owston, Nathan A.; Parker, Alexandra J.; Williams, Jonathan M. J. [Organic Letters, 2007, vol. 9, # 1, p. 73 - 75]
[9]Shang, Sensen; Chen, Pei-Pei; Wang, Lianyue; Lv, Ying; Li, Wei-Xue; Gao, Shuang [ACS Catalysis, 2018, vol. 8, # 11, p. 9936 - 9944]

12
[ 456-22-4 ]
[ 824-75-9 ]

Yield	Reaction Conditions	Operation in experiment
72%	With tris[2-phenylpyridinato-C₂,N]iridium(III); dipotassium hydrogenphosphate; borane-ammonia complex; di-<i>tert</i>-butyl dicarbonate; magnesium chloride In acetonitrile at 20℃; for 36h; Schlenk technique; Irradiation; Green chemistry;
	Multi-step reaction with 2 steps 1: (COCl)2, DMF / CH₂Cl₂ / Heating 2: conc. NH₄OH / ethyl acetate / 0.17 h
	Multi-step reaction with 2 steps 1: thionyl chloride; N,N-dimethyl-formamide / dichloromethane / 24 h / 80 °C / Inert atmosphere 2: ammonium hydroxide / tetrahydrofuran; water / 1 h / 0 °C / Inert atmosphere

	Multi-step reaction with 2 steps 1: thionyl chloride / chloroform / 8 h / Reflux 2: ammonium hydroxide / tetrahydrofuran / 2 h / 20 °C
	With ammonium hydroxide; 1-hydroxy-7-aza-benzotriazole; 1-ethyl-(3-(3-dimethylamino)propyl)-carbodiimide hydrochloride In dichloromethane; N,N-dimethyl-formamide at 20℃; for 16h;	5.A Step A: 4-Fluorobenzamide Into a 500-mL round-bottom flask, were placed 4-fluorobenzoic acid (5.00 g, 35.7 mmol, 1.00 equiv), EDC (7.20 g, 37.6 mmol, 1.05 equiv), HO At (4.90 g, 36.0 mmol, 1.01 equiv), dichloromethane (144 mL), DMF (36 mL). The resulting mixture was stirred for 10 min at ambient temperature followed by the addition of ammonium hydroxide (6.50 g, 46.4 mmol, 1.30 equiv, 25%) dropwise with stirring. The resulting mixture was stirred for 16 h at ambient temperature. The reaction mixture was quenched with aqueous sodium bicarbonate (200 mL) and extracted with dichloromethane (5 x 100 mL). The combined organic layers was washed with water (2 x 500 mL), brine (400 mL), dried (Na2SC>4), filtered, and solvent was evaporated under reduced pressure. This resulted in 3.50 g (crude) of 4-fluorobenzamide as an off-white solid: MS (ES, m/z): 140.1 (M+l).
	With acetic acid; 1-ethyl-(3-(3-dimethylamino)propyl)-carbodiimide hydrochloride In dichloromethane; N,N-dimethyl-formamide at 20℃; for 16h;	5.A 4-Fluorobenzamide Into a 500-mL round-bottom flask, were placed 4-fluorobenzoic acid (5.00 g, 35.7 mmol, 1.00 equiv), EDC (7.20 g, 37.6 mmol, 1.05 equiv), HOAt (4.90 g, 36.0 mmol, 1.01 equiv), dichloromethane (144 mL), DMF (36 mL). The resulting mixture was stirred for 10 mm at ambient temperature followed by the addition of ammonium hydroxide (6.50 g, 46.4 mmol, 1.30equiv, 25%) dropwise with stirring. The resulting mixture was stirred for 16 h at ambient temperature. The reaction mixture was quenched with aqueous sodium bicarbonate (200 mL) and extracted with dichloromethane (5 x 100 mL). The combined organic layers was washed with water (2 x 500 mL), brine (400 mL), dried (Na2SO4), filtered, and solvent was evaporated under reduced pressure. This resulted in 3.50 g (crude) of 4-fluorobenzamide as an off-white solid: MS(ES, m/z): 140.1 (M+1).
	Multi-step reaction with 2 steps 1: triethylamine; thionyl chloride / 1 h / Radiolysis 2: ammonium hydroxide / water; dichloromethane / 4 h / 20 °C
	Multi-step reaction with 2 steps 1: thionyl chloride; N,N-dimethyl-formamide / Reflux 2: ammonium hydroxide / 0 °C
	Multi-step reaction with 2 steps 1: thionyl chloride / 0.5 h / 85 °C / Reflux 2: ammonium hydroxide / dichloromethane / 0.5 h / Cooling with ice
	Multi-step reaction with 2 steps 1: thionyl chloride / toluene / 3 h / Reflux 2: ammonium hydroxide / 1 h / 0 - 10 °C
	Multi-step reaction with 2 steps 1: thionyl chloride; triethylamine / 1 h / Reflux 2: ammonium hydroxide / water; dichloromethane / 4 h / 20 °C
	Stage #1: 4-Fluorobenzoic acid With 1,1'-carbonyldiimidazole In dichloromethane at 20℃; for 0.333333h; Inert atmosphere; Stage #2: With ammonium hydroxide In dichloromethane at 20℃; for 3h; Inert atmosphere;

Reference： [1]Chen, Xuenian; Kang, Jia-Xin; Ma, Yan-Na; Miao, Yu-Qi [Green Chemistry, 2021, vol. 23, # 10, p. 3595 - 3599]
[2]Weikert; Bingham Jr.; Emanuel; Fraser-Smith; Loughhead; Nelson; Poulton [Journal of Medicinal Chemistry, 1991, vol. 34, # 5, p. 1630 - 1633]
[3]Prediger, Patricia; Barbosa, Lais Ferreira; Genisson, Yves; Correia, Carlos Roque Duarte [Journal of Organic Chemistry, 2011, vol. 76, # 19, p. 7737 - 7749]
[4]Yang, Jianzhong; Pi, Weiyi; Xiong, Li; Ang, Wei; Yang, Tao; He, Jun; Liu, Yuanyuan; Chang, Ying; Ye, Weiwei; Wang, Zhenling; Luo, Youfu; Wei, Yuquan [Bioorganic and Medicinal Chemistry Letters, 2013, vol. 23, # 5, p. 1424 - 1427]
[5]Current Patent Assignee: MERCK & CO INC - WO2015/51479, 2015, A1 Location in patent: Page/Page column 69
[6]Current Patent Assignee: MERCK & CO INC - WO2015/54038, 2015, A1 Location in patent: Page/Page column 58; 59
[7]Savolainen, Heli; Cantore, Mariangela; Colabufo, Nicola A.; Elsinga, Philip H.; Windhorst, Albert D.; Luurtsema, Gert [Molecular Pharmaceutics, 2015, vol. 12, # 7, p. 2265 - 2275]
[8]Wang, Sen-Lin; Shi, Yu-Jun; He, Hai-Bing; Li, Yu; Li, Yang; Dai, Hong [Chinese Chemical Letters, 2015, vol. 26, # 6, p. 672 - 674]
[9]Wu, Youzhi; Sun, Peng; Zhang, Kaifan; Yang, Tie; Yao, Hequan; Lin, Aijun [Journal of Organic Chemistry, 2016, vol. 81, # 5, p. 2166 - 2173]
[10]Lei, Peng; Xu, Yan; Du, Juan; Yang, Xin-Ling; Yuan, Hui-Zhu; Xu, Gao-Fei; Ling, Yun [Bioorganic and Medicinal Chemistry Letters, 2016, vol. 26, # 10, p. 2544 - 2546]
[11]Current Patent Assignee: BIOFORDRUG SRL; NETHERLANDS ORGANISATION FOR SCIENTIFIC RESEARCH; VU UNIVERSITY MEDICAL CENTRE AMSTERDAM; UNIVERSITY MEDICAL CENTER GRONINGEN; UNIVERSITY OF GRONINGEN - WO2015/194954, 2015, A1
[12]Sureshbabu, Popuri; Azeez, Sadaf; Muniyappan, Nalluchamy; Sabiah, Shahulhameed; Kandasamy, Jeyakumar [Journal of Organic Chemistry, 2019, vol. 84, # 18, p. 11823 - 11838]

13
paraformaldehyde [ No CAS ]
3-methyl-1',2',3',6'-tetrahydro-2,4'-bipyridine trifluoroacetate salt [ No CAS ]
[ 824-75-9 ]
4-fluoro-N-[(3-methyl-3',6'-dihydro-2,4'-bipyridin-1'(2'H)-yl)methyl]benzamide [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
94%	With potassium carbonate In ethanol Heating / reflux;	218 EXAMPLE 218; 4-fluoro-N-[(3-methyl-3',6'-dihydro-2,4'-bipyridin-1'(2'H)-yl)methyl]benzamide [1661] A mixture of the product from Example 143B (trifluoroacetic acid salt, 29 mg, 0.1 mmol), paraformaldehyde (30 mg, 1 mmol), 4-fluorobenzamide (70 mg, 0.5 mmol, Aldrich), and 42 mg of potassium carbonate (0.3 mmol) in 2.5 mL absolute ethyl alcohol was heated to reflux under nitrogen overnight. The mixture was cooled to room temperature, filtered, and the solvent was removed under reduced pressure under reduced pressure. The residue was purified by flash column chromatography on silica gel (10% methanol:ethyl acetate) to give 30 mg (94%) pure compound. 1H NMR (500 MHz, DMSO-d6) δ2.30 (s, 3H), 2.46 (m, 2H), 2.77 (m, 2H), 3.24 (m, 2H), 4.28 (d, J=5 Hz, 2H), 5.80 (m, 1H), 7.14 (t, J=5 Hz, 1H), 7.30 (t, J=6 Hz, 2H), 7.58 (d, J=5 Hz, 1H), 7.98 (t, J=6 Hz, 2H), 8.34 (d, J=5 Hz, 1H), 8.85 (t, J=5 Hz, 1H); MS (ESI APCI-) m/e 324 (M-H)+.

Reference： [1]Current Patent Assignee: ABBVIE INC - US2003/229094, 2003, A1 Location in patent: Page 101-102

14
[ 824-75-9 ]
[ 402-46-0 ]
[ 21655-48-1 ]
[ 170858-10-3 ]

Yield	Reaction Conditions	Operation in experiment
		Example 143 (S)-(-)-4-[4-[2-(Isochroman-1-yl)ethyl]-cis-3,5-dimethylpiperazin-1-yl]benzenesulfonamide (LXXXI) Following the general procedure of EXAMPLE 49 and making non-critical variations 2-(isochroman-1-yl)ethanol-O-methanesulfonate (LXXX, 0.412 g) and 4-(3,5-dimethylpiperazin-1-yl)benzenesulfonamide ?(IV), 0.433 g; prepared from <strong>[402-46-0]4-fluorobenzenesulfonamide</strong>, III, and cis-2,6-dimethylpiperazine, II (Aldrich), by the method of EXAMPLE 47! gives the title compound; mp 170-175(decomp); MS (m/z) 429; IR (mineral oil) 1153, 1596, 1325, 1162 and 1096 cm-1.

Reference： [1]Patent: US5877317,1999,A

15
[ 824-75-9 ]
[ 109-07-9 ]
(RS)-4-(3-methylpiperazin-1-yl)benzamide [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	In water;	Step 1. (RS)-4-(3-Methylpiperazin-1-yl)benzamide. Refer to Chart C A mixture of 4-fluorobenzamide (Aldrich; 2.432 g), <strong>[109-07-9](RS)-2-methylpiperazine</strong> (Aldrich; 4.247 g), and water (9 mL) is heated at 100 C. for 7 days. The mixture is then cooled to 41 C. and water is added. The solid is collected, washed with water and toluene and dried under reduced pressure to give 3.37 g of (RS)-4-(3-methylpiperazin-1-yl)benzamide; 1 H NMR (CDCl3, CD3 OD) delta1.17, 2.48, 2.82, 2.94-3.15, 3.04, 3.68, 6.89, 7.73.

Reference： [1]Patent: US5912246,1999,A

16
[ 824-75-9 ]
[ 349-88-2 ]
[ 433-14-7 ]

Yield	Reaction Conditions	Operation in experiment
	With methylamine hydrochloride; triethylamine; In tetrahydrofuran;	Example 152 N-Methyl-(S)-(-)-4-[4-[2-(isochroman-1-yl)ethyl]piperazin-1-yl]benzenesulfonamide N-Methyl-4-fluorobenzenesulfonamide (III) A mixture of 4-fluorobenzenesulfonyl chloride (III, Aldrich, 3.12 g), methylamine hydrochloride (1.17 g), triethylamine (4.8 ml) and THF (25 ml) are stirred at 20-25 for five days. The mixture is then partitioned between dichloromethane, aqueous sodium bicarbonate, and saline. The organic phases are dried over magnesium sulfate and concentrated. The resulting solid is crystallized from dichloromethane/hexane and then recrystallized from methanol/dichloromethane to give N-methyl-4-fluorobenzenesulfonamide, NMR 2.67, 4.55, 7.21, 7.89 delta.

Reference： [1]Patent: US5877317,1999,A

17
[ 110-85-0 ]
[ 824-75-9 ]
[ 116290-73-4 ]

Yield	Reaction Conditions	Operation in experiment
82%	In water at 100℃;	1 Compound 6 (1.40 g, 10.0 mmol) and Compound 7 (4.6 g, 53.1 mmol) were added to water (10 mL) and stirred at 100 ° C overnight. After completion of the reaction, the mixture was cooled to room temperature, and a solid was precipitated, filtered, washed with water, toluene, and dried to give Compound 8 (1.68 g, 82%).
	In water	3.1 Step 1. Step 1. 4-(Piperazin-1-yl)benzamide. Refer to Chart C A mixture of piperazine (7.56 g) and 4-fluorobenzamide (2.44 g) in water (10 mL) is heated at reflux for 27 h. The mixture is then allowed to cool slightly and the solid is collected and washed with water and dichloromethane, followed by drying to give 3.24 g of 4-(piperazin-1-yl)benzamide; mp 238-243° C.; ms m/z 205; IR (mineral oil) 1609, 1255, 1665, 1389, 3149 cm-1. 1 H NMR (DMSOd6) δ2.59, 2.80, 3.14, 6.90, 7.02, 7.72, 7.73.

Reference： [1]Current Patent Assignee: SHANGHAI MEDICILON - CN108570039, 2018, A Location in patent: Paragraph 0123
[2]Current Patent Assignee: PFIZER INC - US5912246, 1999, A

18
[ 824-75-9 ]
[ 99-97-8 ]
[ 1042709-43-2 ]

Yield	Reaction Conditions	Operation in experiment
81%		General procedure: A 15 mL round-bottom flask was charged with a stirring bar, 2.0 mL ethyl acetate, N,N-dimethylaniline derivative (0.9 mmol), amide (0.5 mmol) and complex 2 (27.9 mg, 0.05 mmol) were added. After stirring 15 min, TBHP (0.75 mmol, 108 mL) was added without extrusion of the air. The mixture was stirred for 8 h at 40 oC. After cooling to room temperature, 10 mL ethyl acetate was added, and the mixture was filtered. The filtrate was concentrated, and the residue was purified by column chromatography on silica gel using ethyl acetate/pet ether (60-90 oC) as eluent to give the desired product.

Reference： [1]Tetrahedron Letters,2016,vol. 57,p. 4152 - 4156
[2]Journal of Organic Chemistry,2008,vol. 73,p. 6207 - 6212

19
[ 824-75-9 ]
[ 32996-16-0 ]
[ 1095885-49-6 ]

Reference： [1]Tetrahedron Letters,2008,vol. 49,p. 7328 - 7329

20
[ 824-75-9 ]
[ 536-74-3 ]
4-fluoro-N-[(Z)-2-phenylvinyl]benzamide [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
93%	With [bis(2-methylallyl)cycloocta-1,5-diene]ruthenium(II); 1,4-bis(dicyclohexylphosphino)butane; ytterbium(III) triflate In water; N,N-dimethyl-formamide at 60℃; for 6h; Inert atmosphere; optical yield given as %de; stereoselective reaction;

Reference： [1]Goossen, Lukas J.; Salih, Kifah S. M.; Blanchot, Mathieu [Angewandte Chemie - International Edition, 2008, vol. 47, # 44, p. 8492 - 8495]

21
[ 1063716-69-7 ]
[ 824-75-9 ]

Yield	Reaction Conditions	Operation in experiment
78%	With Selectfluor In acetonitrile at 50℃; for 0.5h;	5 [00612] After fluorination had been carried out, all volatiles from the sample were removed on high-vac and the Pd-residue was analyzed by NMR.

Reference： [1]Current Patent Assignee: HARVARD UNIVERSITY - WO2009/100014, 2009, A1 Location in patent: Page/Page column 171-173; 193

22
[ 403-42-9 ]
[ 824-75-9 ]

Yield	Reaction Conditions	Operation in experiment
94%	With ammonia; water; iodine In tetrahydrofuran at 20℃; for 1h;
90%	With ammonia; iodine In water at 60℃; for 1h;
59%	With tert.-butylhydroperoxide; ammonia; tetra-(n-butyl)ammonium iodide In water at 100℃; for 16h; Green chemistry;

58%	With sodium azide; iodine; sodium hydrogencarbonate In water at 100℃; for 2h;
58%	With sodium azide; 2,2,6,6-Tetramethyl-1-piperidinyloxy free radical; oxygen; copper dichloride In water; N,N-dimethyl-formamide at 120℃; for 15h; Schlenk technique; chemoselective reaction;

Reference： [1]Location in patent: experimental part Angeles, Norma A.; Villavicencio, Felipe; Guadarrama, Carlos; Corona, David; Cuevas-Yañez, Erick [Journal of the Brazilian Chemical Society, 2010, vol. 21, # 5, p. 905 - 908]
[2]Cao, Liping; Ding, Jiaoyang; Gao, Meng; Wang, Zihua; Li, Juan; Wu, Anxin [Organic Letters, 2009, vol. 11, # 17, p. 3810 - 3813]
[3]Sharif, Muhammad; Chen, Jianbin; Langer, Peter; Beller, Matthias; Wu, Xiao-Feng [Organic and Biomolecular Chemistry, 2014, vol. 12, # 33, p. 6359 - 6362]
[4]Rajendar; Kant, Ruchir; Narender [Advanced Synthesis and Catalysis, 2013, vol. 355, # 18, p. 3591 - 3596]
[5]Tang, Conghui; Jiao, Ning [Angewandte Chemie - International Edition, 2014, vol. 53, # 25, p. 6528 - 6532][Angew. Chem., 2014, vol. 126, # 25, p. 6646 - 6650,5]

23
[ 591-50-4 ]
[ 824-75-9 ]
[ 366-63-2 ]

Yield	Reaction Conditions	Operation in experiment
65%	With potassium carbonate; N,N`-dimethylethylenediamine; In toluene; at 110℃; for 48h;Schlenk technique; Inert atmosphere;	General procedure: An oven-dried Schlenk tube was charged with benzamide 1 (0.5 mmol), K2CO3 (207 mg, 1.5 mmol) and aryl iodide 2 (1.0 mol). The tube was evacuated and backfilled with N2 (3 ×), and then DMEDA (0.2 mmol) and anhyd toluene (5.0 mL) were added. The reaction mixture was stirred at 110 C for 48 h. H2O was added and the crude product was extracted with EtOAc. The combined organic phases were washed with brine and H2O, dried (Na2SO4), and concentrated under reduced pressure. The product was purified by silica gel chromatographyto give the desired N-arylated benzamides (Table 2).

Reference： [1]Synlett,2009,p. 2663 - 2668
[2]Synthesis,2018,vol. 50,p. 1090 - 1096

24
[ 637-87-6 ]
[ 824-75-9 ]
[ 1978-88-7 ]

Yield	Reaction Conditions	Operation in experiment
92%	With potassium carbonate; N,N`-dimethylethylenediamine; In toluene; at 110℃; for 48h;Schlenk technique; Inert atmosphere;	General procedure: An oven-dried Schlenk tube was charged with benzamide 1 (0.5 mmol), K2CO3 (207 mg, 1.5 mmol) and aryl iodide 2 (1.0 mol). The tube was evacuated and backfilled with N2 (3 ×), and then DMEDA (0.2 mmol) and anhyd toluene (5.0 mL) were added. The reaction mixture was stirred at 110 C for 48 h. H2O was added and the crude product was extracted with EtOAc. The combined organic phases were washed with brine and H2O, dried (Na2SO4), and concentrated under reduced pressure. The product was purified by silica gel chromatographyto give the desired N-arylated benzamides (Table 2).

Reference： [1]Synthesis,2018,vol. 50,p. 1090 - 1096
[2]Synlett,2009,p. 2663 - 2668

25
[ 459-23-4 ]
[ 824-75-9 ]

Yield	Reaction Conditions	Operation in experiment
99%	With C₅₅H₄₅ClN₅P₂Ru⁽¹⁺⁾*Cl^(1-) In water at 110℃; for 12h; Sealed tube;
95%	With [(eta.⁽⁵⁾-pentamethylcyclopentadienyl)Ir(H₂O)3](OTf)2 In water at 110℃; for 12h; Schlenk technique;
95%	With [(eta.⁽⁵⁾-pentamethylcyclopentadienyl)Ir(H₂O)3](OTf)2 In water at 110℃; for 12h; Schlenk technique;	8 4-fluorobenzamide To a stirred solution of 4-fluorobenzaldehyde oxime (69.6 mg, 0.5 mmol), [Cp * Ir (H20) 3] [0Tf] 2 (5.0 mg, 0.0075 mmol, (1 ml) were added sequentially to a 25 ml Schlenk reaction flask. The reaction mixture was allowed to react at 110 ° C for 12 hours, then cooled to room temperature. The water was removed by rotary evaporation, and the product was isolated by column chromatography. Yield: 95%. 2H, ArH), 7.41 (br s, 1H, NH), 7.95-7.92 (m, 2H, ArH) (D, JCF = 246. 8 H z), 130.7 (d, JcF = l.9 & lt; RTIgt; z), & lt; / RTI & gt; ), 130. 0 (d, Jc F = 9. O ζ), 115. 0 (d, Jc F = 21.4 ζζ).

89%	With cis,cis,trans-[RuCl₂{κ²-(P,N)-2-Ph₂PC₆H₄CH=NOH}₂] In water at 100℃; for 4h; Sealed tube; Inert atmosphere;
87%	With [Ru(OTf){η⁶:κ¹(P)-PPh₂-binaphthyl}{PPh₂(OH)}][OTf] In water at 100℃; for 6h; Inert atmosphere; Sealed tube;
86%	With [RuCl₂(η²-C₆H₆){P(NMe₂)₃}]; water at 100℃; for 5h; Inert atmosphere; Sealed tube;
85%	With silver tetrafluoroborate; chloro(1,3-bis(2,6-di-i-propylphenyl)imidazol-2-ylidene)gold(I) at 100℃; for 20h; Sealed tube; Neat (no solvent);
85%	With copper diacetate; acetonitrile In ethanol at 78℃; for 6h; chemoselective reaction;	Preparation of amides from aldoximes; general procedures General procedure: To a 25 mL round-bottom flask equipped with a magnetic stirrer were added aldoximes (5 mmol), copper(II) acetate (45 mg, 0.25 mmol),acetonitrile (10 mg, 0.25 mmol) and EtOH (15 mL). The mixture was stirred for 4-8 h at 78 °C or for 12 h at room temperature. After removal of the solvent, the residue was purified by column chromatography to afford the desired product.
75%	With copper diacetate In toluene at 80℃; for 24h;	2. Typical procedure for the use of a homogeneous catalyst General procedure: To a clean, oven dried reaction vessel was added a clean stirrer bar followed by 3 mmol of the required oxime. To this was added either 1 or 2 mol% Cu(OAc)2 (0.0060g / 0.0120g respectively), followed by toluene (0.75 mL) The vessel was gently warmed and allowed to stir for approximately 5 minutes or until dissolution was complete. The vessels were placed into the preheated carousel (80°C) and run simultaneously for 24 hours.Following reaction the tubes were promptly removed and allowed to cool. The vessel was opened and contents diluted using sufficient dichloromethane (20 mL). The reaction products were then concentrated in vacuo and a crude sample submitted for NMR. Isolated yields were obtained using column chromatography through 35-70 micron dry silica using EtOAc: Hexane (3:1) as eluent. These were confirmed by NMR.

Reference： [1]Yang, Fa-Liu; Zhu, Xinju; Rao, Dun-Kang; Cao, Xiao-Niu; Li, Ke; Xu, Yan; Hao, Xin-Qi; Song, Mao-Ping [RSC Advances, 2016, vol. 6, # 43, p. 37093 - 37098]
[2]Sun, Chunlou; Qu, Panpan; Li, Feng [Catalysis science and technology, 2014, vol. 4, # 4, p. 988 - 996]
[3]Current Patent Assignee: NANJING UNIVERSITY OF SCIENCE AND TECHNOLOGY - CN104418682, 2016, B Location in patent: Paragraph 0051-0055
[4]Francos, Javier; Menéndez-Rodríguez, Lucía; Tomás-Mendivil, Eder; Crochet, Pascale; Cadierno, Victorio [RSC Advances, 2016, vol. 6, # 45, p. 39044 - 39052]
[5]Toms-Mendivil, Eder; Menndez-Rodrguez, Luca; Francos, Javier; Crochet, Pascale; Cadierno, Victorio [RSC Advances, 2014, vol. 4, # 108, p. 63466 - 63474]
[6]Garcia-Alvarez, Rocio; Diaz-Alvarez, Alba E.; Borge, Javier; Crochet, Pascale; Cadierno, Victorio [Organometallics, 2012, vol. 31, # 17, p. 6482 - 6490]
[7]Location in patent: experimental part Ramon, Ruben S.; Bosson, Johann; Diez-Gonzalez, Silvia; Marion, Nicolas; Nolan, Steven P. [Journal of Organic Chemistry, 2010, vol. 75, # 4, p. 1197 - 1202]
[8]Ma, Xiaoyun; Lu, Ming [Journal of Chemical Research, 2016, vol. 40, # 10, p. 594 - 596]
[9]Sharma, Sumeet K.; Bishopp, Simon D.; Liana Allen; Lawrence, Ruth; Bamford, Mark J.; Lapkin, Alexei A.; Plucinski, Pawel; Watson, Robert J.; Williams, Jonathan M.J. [Tetrahedron Letters, 2011, vol. 52, # 33, p. 4252 - 4255]

26
[ 824-75-9 ]
[ 301221-79-4 ]
[ 1207747-34-9 ]

Yield	Reaction Conditions	Operation in experiment
	In N,N-dimethyl-formamide; at 145℃; for 16h;	INTERMEDIATE 344-[2-(4-Fluoropheny1H3-oxazol-4-yl]piperidineA solution of 4-fluorobenzamide (4.54 g, 32.7 mmol) and /-butyl 4-(bromoacetyl)-piperidine-1- carboxylate (5.0 g, 16.3 mmol) in DMF (40 mL) was heated at 145°C for 16 h. Upon completion of the reaction, the solution was allowed to cool to rt and concentrated to a dark oil. The oil was purified by reverse phase HPLC to afford the title compound (760 mg). LC/MS: m/e 247.08 (M+H).div..
	In N,N-dimethyl-formamide; at 145℃; for 16h;	A solution of 4-fluorobenzamide (4.54 g, 32.7 mmol) and t-butyl 4-(bromoacetyl)-piperidine-1-carboxylate (5.0 g, 16.3 mmol) in DMF (40 mL) was heated at 145'C for 16 h. Upon completion of the reaction, the solution was allowed to cool to rt and concentrated to a dark oil. The oil was purified by reverse phase HPLC to afford the title compound (760 mg). LC/MS: m/e 247.08 (M+14)+.

Reference： [1]Patent: WO2010/17079,2010,A1 .Location in patent: Page/Page column 65-66
[2]Patent: US2011/21531,2011,A1 .Location in patent: Page/Page column 31

27
[ 887581-09-1 ]
[ 824-75-9 ]
[ 1255516-32-5 ]

Reference： [1]Journal of Organic Chemistry,2010,vol. 75,p. 7936 - 7938

28
[ 824-75-9 ]
[ 67496-29-1 ]
[ 1255516-37-0 ]

Reference： [1]Journal of Organic Chemistry,2010,vol. 75,p. 7936 - 7938

29
[ 696-59-3 ]
[ 824-75-9 ]
[ 90172-61-5 ]

Yield	Reaction Conditions	Operation in experiment
65%	With magnesium iodide etherate In acetonitrile at 80℃; for 10h; chemoselective reaction;	3.2. General procedure for preparation of N-acyl pyrrole 5a-e General procedure: A Schlenk reaction tube was charged with primary aromatic amide (5.0 mmol), 2,5-dimethoxytetrahydrofuran (6.0 mmol), MgI2 etherate (10% mmol), and acetonitrile (10 mL). The reaction mixture was stirred at 80 °C for several hours and then concentrated in vacuo. The residue was purified by flash column chromatography on a silica gel to give the desired product.

Reference： [1]Location in patent: experimental part Zhang, Xingxian; Shi, Junchen [Tetrahedron, 2011, vol. 67, # 5, p. 898 - 903]

30
[ 754131-60-7 ]
[ 824-75-9 ]
[ 1300022-20-1 ]

Yield	Reaction Conditions	Operation in experiment
	With sodium hydride; In tetrahydrofuran; mineral oil; for 24h;Reflux;	To a mixture of 3 -bromo-2-bromomethyl -pyridine (1.30 g, 5.18 mmol) and 4-fluoro- benzamide (725 mg, 5.21 mmol) in THF (20 mL) is added 60% sodium hydride in mineral oil (210 mg, 5.3 mmol) and the mixture is warmed at reflux. After 24 hours, the mixture is diluted with saturated aqueous ammonium chloride (25 mL) and extracted with ethyl acetate (2 x 25 mL). The combined organic layers are washed with brine (2 x 25 mL), dried over magnesium sulfate, filtered and concentrated. The residue is purified by silica gel chromatography eluting using a gradient of 5-25% EtOAc in hexanes to afford N-(3-bromopyridin-2-ylmethyl)-4-fluoro-benzamide.

Reference： [1]Patent: WO2011/56440,2011,A1 .Location in patent: Page/Page column 32-33

31
[ 824-75-9 ]
[ 140-75-0 ]

Yield	Reaction Conditions	Operation in experiment
72%	Stage #1: p-fluorobenzamide With bis(cyclopentadienyl)dihydrozirconium; 4,4,5,5-tetramethyl-[1,3,2]-dioxaboralane at 20℃; Glovebox; Inert atmosphere; Stage #2: With hydrogenchloride In diethyl ether; water for 2h; Glovebox; Inert atmosphere;	2. Experimental General procedure: In a nitrogen-filled glovebox, to a 15 mL reaction tube equipped with a magnetic stirrer, were added Cp2ZrH2 (0.01mmol, 2.2 mg) as the catalyst, and the appropriate amide (0.2mmol); solvent was added when necessary. HBpin (3 equiv. peramide functional group) was then added, and the reaction tube was taken out from the glovebox and stirred at room temperature for 12-48 h. The resultant crude amines were either isolated using silica gel flash chromatography, or acidified by stirring with HCl in Et2O (2 mL, 1N) for 2 h, after which time precipitation was observed. Then, the reaction solution was transferred to a centrifuge tube and centrifuged three times. The supernatant was removed and the resulting solid was dried inan oven at 80 °C for several hours to obtain the HCl salt of the amine.
63 %Chromat.	With 1,10-Phenanthroline; diethoxymethylane; iron(II) acetate In toluene at 100℃; for 28h; Inert atmosphere; chemoselective reaction;
	With 4,4,5,5-tetramethyl-[1,3,2]-dioxaboralane In neat (no solvent) at 120℃; for 24h; Inert atmosphere; Sealed tube; chemoselective reaction;	General procedure for hydroboration of primary amides General procedure: Benzamide (0.0606 g, 0.5 mmol) was placed in a culture tube (11 mL) at 25 °C, sealed with septum, the air in culture tube was replaced with argon gas (Tables 1 and 2). After adding pinacolborane (0.36 ml, 2.5 mmol 5 equiv), the screw cap was closed, stirred at 120 °C for 24 h. After this time, it was cooled to room temperature, excess HBpin was quenched by adding water (0.5 ml). The mixture was diluted with ethyl acetate (5 ml), 1 M HCl in ether (2 ml) and stir for 1 h. The generated amine salt was filtered using ethyl acetate.

Reference： [1]Han, Bo; Jiao, Haijun; Wu, Lipeng; Zhang, Jiong [Cuihua Xuebao/Chinese Journal of Catalysis, 2021, vol. 42, # 11, p. 2059 - 2067]
[2]Das, Shoubhik; Wendt, Bianca; Moeller, Konstanze; Junge, Kathrin; Beller, Matthias [Angewandte Chemie - International Edition, 2012, vol. 51, # 7, p. 1662 - 1666]
[3]Yi, Jaeeun; Kim, Hyun Tae; Jaladi, Ashok Kumar; An, Duk Keun [Bulletin of the Korean Chemical Society, 2022, vol. 43, # 1, p. 129 - 132]

32
[ 352-34-1 ]
[ 201230-82-2 ]
[ 824-75-9 ]

Yield	Reaction Conditions	Operation in experiment
95%	With ammonium hydroxide; 1,3,5,7-tetramethyl-2,4,8-trioxa-6-phenyl-6-phosphaadamantane; palladium diacetate; In toluene; at 100℃; under 5171.62 Torr; for 20h;Autoclave;	General procedure: To a 45 mL glass-lined autoclave, 1 (0.5 mmol), Pd(OAc)2 (0.01mmol), CYTOP292 (0.02mmol), aqueous ammonia (0.2 mL) and toluene (10 mL) were sequentially added. After sealing, the autoclave was purged three times with carbon monoxide and pressurized with 100 psi of CO. The resulting mixture was then heated at 100 C for 20 h. The autoclave was removed from the oil bath and cooled to room temperature prior to the release of excess carbon monoxide. The reaction mixture was concentrated by rotary evaporator, and purified by flash chromatography on silica gel with a mixture of hexanes and ethyl acetate (2:1to 1:2) as the eluent to afford the products.

Reference： [1]Tetrahedron Letters,2013,vol. 54,p. 5496 - 5499
[2]Angewandte Chemie - International Edition,2012,vol. 51,p. 3668 - 3672

33
[ 50877-41-3 ]
[ 824-75-9 ]
[ 1052660-25-9 ]

Reference： [1]Angewandte Chemie - International Edition,2012,vol. 51,p. 4710 - 4713

34
[ 824-75-9 ]
[ 18087-73-5 ]
[ 1380248-43-0 ]

Reference： [1]Angewandte Chemie - International Edition,2012,vol. 51,p. 4710 - 4713

35
[ 140-75-0 ]
[ 824-75-9 ]

Yield	Reaction Conditions	Operation in experiment
85%	With tert.-butylhydroperoxide; caesium carbonate; In water; acetonitrile; for 4h;Reflux;	General procedure: To a solution of 4-methoxybenzyl amine (1.0 mmol) and cesium carbonate (1.0 mmol) in 3 mL of CH3CN was added a solution of 70% aqueous TBHP (3.0 mmol) and the mixture was refluxed for 4 h. The mixture was then dried to vacuum and extracted three times with ethyl acetate followed by washing with brine,and dried over anhydrous Na2SO4. Evaporation of the solvent under vacuum afforded the crude product, which was furthur purified by column chromatography using hexane/ethyl acetate mixture and then analyzed by spectroscopy.
	With manganese(IV) oxide; oxygen; In dichloromethane; at 180℃; under 15001.5 Torr; for 24h;	Add 300 mg of manganese dioxide, 60 mg of p-fluorobenzylamine in 6 g of dichloromethane (mass concentration in the mixture:1.0%), uniformly mixed; charged with 2 MPa of oxygen, reacted at 180 C for 24 hours, the conversion of p-fluorobenzylamine was 98.4%, and the selectivity of the corresponding p-fluorobenzamide was 99.0%.

Reference： [1]Dalton Transactions,2020,vol. 49,p. 3480 - 3487
[2]Chemistry - A European Journal,2018,vol. 24,p. 1067 - 1071
[3]Tetrahedron Letters,2019,vol. 60
[4]Green Chemistry,2019,vol. 21,p. 962 - 967
[5]Chemical Communications,2012,vol. 48,p. 12237 - 12239
[6]Journal of Organic Chemistry,2018,vol. 83,p. 260 - 266
[7]Journal of Organic Chemistry,2017,vol. 82,p. 13632 - 13642
[8]Synlett,2012,vol. 23,p. 801 - 804
[9]Patent: CN108610226,2018,A .Location in patent: Paragraph 0075; 0076
[10]ChemCatChem,2019,vol. 11,p. 401 - 406

36
[ 824-75-9 ]
[ 1515-95-3 ]
[ 701239-56-7 ]

Reference： [1]Organic and biomolecular chemistry,2012,vol. 10,p. 9137 - 9141,5

37
[ 201230-82-2 ]
[ 460-00-4 ]
[ 824-75-9 ]

Yield	Reaction Conditions	Operation in experiment
	With ammonia; palladium diacetate; catacxium A In 1,4-dioxane at 100℃; for 16h; Autoclave;	Typical reaction procedure for the synthesis of 2-phenylbenzoxazole General procedure: A 12 mL vial was charged with Pd(OAc)2 (2 mol%), BuPAd2 (6 mol%), and a stirring bar. Then, 2 ml dioxane and 1 mmol of bromobenzene were injected by syringe. The vial (or several vials) was placed in an alloy plate, which was transferred into a 300 mL autoclave of the 4560 series from Parr Instruments under argon atmosphere. After flushing the autoclave three times with NH3, a pressure of 2 bar NH3 and 2 bar CO was adjusted at ambient temperature. Then, the reaction was performed for 16 hours at 100 oC. After the reaction is finished, the autoclave was cooled down to room temperature and the pressure was released carefully. Then, CuI (5 mol%), DMEDA (10%), K2CO3 (3 mmol) and 1,2-dibromobenzene were added in under air, the vial was closed and heated to 110oC for 20 hours. The reaction mixture cooled down to room temperature. The solution was extracted 3-5 times with 2-3 ml of ethyl acetate from aqua solution. After evaporation of the organic solvent the residue was adsorbed on silica gel and the crude product was purified by column chromatography using n-heptane/AcOEt (20:1) as eluent.

Reference： [1]Wu, Xiao-Feng; Neumann, Helfried; Neumann, Stephan; Beller, Matthias [Tetrahedron Letters, 2013, vol. 54, # 24, p. 3040 - 3042]

38
C₇H₆BF₃NO^(1-)*K⁽¹⁺⁾ [ No CAS ]
[ 824-75-9 ]
[ 455-37-8 ]

Reference： [1]Journal of the American Chemical Society,2013,vol. 135,p. 14012 - 14015

39
[ 824-75-9 ]
[ 1122-91-4 ]
N,N'-((4-bromophenyl)methylene)bis(4-fluorobenzamide) [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
90%	With boron trifluoride diethyl etherate In acetone at 20℃; for 0.5h; Inert atmosphere;	General procedure 1 for thepreparation of bisamide in acetone General procedure: Acetone (5.0 mL) was added to the mixture of amide (2.0 mmol) and aldehyde (1.0mmol), followed by the addition of BF3 etherate (12.6 μL, 0.1 mmol).Then the mixture was stirred at room temperature until the full consumption ofstarting material detected by TLC analysis. Then the product was collected assolid by filtration and washed with a small portion of diethyl ether. After drying under vacuum, the purity was checked by 1HNMR: only desired peaks were observed except minor solvent residue in only afew cases.

Reference： [1]Zhang, Yi; Zhong, Zhihao; Han, Yingmei; Han, Ruirui; Cheng, Xu [Tetrahedron, 2013, vol. 69, # 52, p. 11080 - 11083]

40
[ 824-75-9 ]
[ 122-78-1 ]
N,N'-(2-phenylethane-1,1-diyl)bis(4-fluorobenzamide) [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
90%	With boron trifluoride diethyl etherate In acetone at 20℃; for 0.666667h; Inert atmosphere;	General procedure 1 for thepreparation of bisamide in acetone General procedure: Acetone (5.0 mL) was added to the mixture of amide (2.0 mmol) and aldehyde (1.0mmol), followed by the addition of BF3 etherate (12.6 μL, 0.1 mmol).Then the mixture was stirred at room temperature until the full consumption ofstarting material detected by TLC analysis. Then the product was collected assolid by filtration and washed with a small portion of diethyl ether. After drying under vacuum, the purity was checked by 1HNMR: only desired peaks were observed except minor solvent residue in only afew cases.

Reference： [1]Zhang, Yi; Zhong, Zhihao; Han, Yingmei; Han, Ruirui; Cheng, Xu [Tetrahedron, 2013, vol. 69, # 52, p. 11080 - 11083]

41
[ 110-62-3 ]
[ 824-75-9 ]
N,N'-(pentane-1,1-diyl)bis(4-fluorobenzamide) [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
93%	With boron trifluoride diethyl etherate In acetone at 20℃; for 0.5h; Inert atmosphere;	General procedure 1 for thepreparation of bisamide in acetone General procedure: Acetone (5.0 mL) was added to the mixture of amide (2.0 mmol) and aldehyde (1.0mmol), followed by the addition of BF3 etherate (12.6 μL, 0.1 mmol).Then the mixture was stirred at room temperature until the full consumption ofstarting material detected by TLC analysis. Then the product was collected assolid by filtration and washed with a small portion of diethyl ether. After drying under vacuum, the purity was checked by 1HNMR: only desired peaks were observed except minor solvent residue in only afew cases.

Reference： [1]Zhang, Yi; Zhong, Zhihao; Han, Yingmei; Han, Ruirui; Cheng, Xu [Tetrahedron, 2013, vol. 69, # 52, p. 11080 - 11083]

42
[ 111-86-4 ]
[ 824-75-9 ]
[ 544661-08-7 ]

Yield	Reaction Conditions	Operation in experiment
90%	With Fe³⁺ exchanged montmorillonite K-10 In neat (no solvent) at 140℃; for 30h; Inert atmosphere;	General procedure: A typical procedure for transamidation of benzamide with n-octylamineis as follows. Fe-mont (121.4mg, 1.0 mol% Fe-mont with respect to benzamide) was added to the mixture of benzamide (1.0 mmol), n-octylamine (1.1 mmol) in a reaction vessel equipped with a condenser under N2. The resulting mixture was vigorously stirred at 140 °C. The reaction mixture was analyzed by GC.Conversion and yield of the products were determined based on benzamide and n-octyl benzamide using dodecane as an internal standard. After completion of the reaction, acetone (2 g) was added to the mixture, and then the Fe-mont catalyst was separated by centrifugation. The crude product was isolated by column chromatography and the resulting product was identified by GCMS, 1H-NMR and 13C-NMR analyses.

Reference： [1]Ayub Ali, Md.; Hakim Siddiki; Kon, Kenichi; Shimizu, Ken-Ichi [Tetrahedron Letters, 2014, vol. 55, # 7, p. 1316 - 1319]

43
[ 405-50-5 ]
[ 824-75-9 ]

Yield	Reaction Conditions	Operation in experiment
67%	With ammonium hydroxide; oxygen In neat (no solvent) at 120℃; for 6h; Sealed tube;	General Procedure for preparation of amides catalyzed by Fe₃O_4SiO₂-SMTU-Cu General procedure: A sealed pressure vessel was charged with phenylacetic acids (68.0 mg, 0.5 mmol), Fe3O4SiO2-SMTU-Cu catalyst (20 mg), and aqueous ammonia solution (28 wt% in H2O; 1.5 mL). The resulting solution was stirred at 120 °C under O2 (monitored by TLC and GC) for 6 hours. Upon completion of the reaction, the catalyst was separated using magnetic stirring bar and ethyl acetate (20 mL) was added, the organic layer was washed with saturate NaHCO3 (20 mL) solution twice, brine (20 mL) once, the combined aqueous layers was extracted with EtOAc (20 mL) twice. The combine organic layers were dried over anhydrous Na2SO4. The solvents were removed via rotary evaporator and the residue was purified with flash chromatography (silica gel, ethyl acetate: petroleum ether=2:1) to give amide products.
55%	With copper oxide (I); ammonium hydroxide; oxygen In lithium hydroxide monohydrate at 130℃; for 40h;

Reference： [1]Riadi, Yassine; M. Kadhim, Mustafa; Jawad Shoja, Sarah; Hussein Ali, Muneam; Fakri Mustafa, Yasser; Sajjadi, Ahmad [Synthetic Communications, 2022, vol. 52, # 6, p. 875 - 887]
[2]Song, Qiuling; Feng, Qiang; Yang, Kai [Organic Letters, 2014, vol. 16, # 2, p. 624 - 627]

44
[ 32222-45-0 ]
[ 824-75-9 ]

Reference： [1]Organic Letters,2014,vol. 16,p. 624 - 627

45
[ 824-75-9 ]
[ 100-51-6 ]
[ 725-38-2 ]

Yield	Reaction Conditions	Operation in experiment
87%	With bis[dichloro(pentamethylcyclopentadienyl)iridium(III)]; caesium carbonate; In toluene; at 130℃; for 12h;	4-Fluorobenzene (121 mg, 1 mmol), [(IPr) AuNTf] (17 mg, 0.02 mmol, 2 mol%), tetrahydrofuran (0.5 ml) and H20 (0.5 ml) were added sequentially to a 25 ml Schlenk reaction flask. After the mixture was allowed to react at 130 C for 12 hours,After cooling to room temperature, the solvent was removed under reduced pressure in vacuo.[Cp * IrCl2] 2 (8 mg, 0. Olmmol, lmol%),benzyl alcohol(130 mg, 1.2 mmol),Cesium carbonate (65 mg, 0.2 equiv.) And toluene(Lml) was added to the reaction flask,The mixture was allowed to continue at 130 C for 12 hours and then cooled to room temperature. The solvent was removed by rotary evaporation, and then purified by column chromatography (developing solvent: ethyl acetate / petroleum ether) to give the title compound in a yield of 87%.

Reference： [1]Chinese Chemical Letters,2020,vol. 31,p. 701 - 705
[2]Chemical Science,2015,vol. 6,p. 1719 - 1727
[3]Patent: CN105820061,2016,A .Location in patent: Paragraph 0120-0123
[4]Journal of Organic Chemistry,2018,vol. 83,p. 3378 - 3384
[5]Green Chemistry,2016,vol. 18,p. 3940 - 3944
[6]Chemical Communications,2014,vol. 50,p. 8303 - 8305
[7]Catalysis science and technology,2015,vol. 5,p. 1953 - 1960

46
[ 924-44-7 ]
[ 824-75-9 ]
ethyl 2-(4-fluorobenzamido)-2-hydroxyacetate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
91%	With diphenyl hydrogen phosphate; In diethyl ether; toluene; at 20℃; for 18h;	General procedure: To a reaction vial charged with amide (1.0mmol), glyoxylate (1.0 mmol), and diphenyl hydrogen phosphate (25.0 mg, 0.1 mmol) was added Et2O (4 mL). Then the sealed reaction mixture was stirred at r.t. for the specified time. The obtained slurry was then filtered, and the precipitate was washed with a minimum amount of cold Et2O to give the compound as a white powder.
91%	With diphenyl hydrogen phosphate; In diethyl ether; toluene; at 20℃; for 18h;Sealed tube;	General procedure: To a reaction vial charged with amide (1.0mmol), glyoxylate (1.0 mmol), and diphenyl hydrogenphosphate (25.0 mg, 0.1 mmol) was added Et2O (4 mL).Then the sealed reaction mixture was stirred at r.t. for the specified time. The obtained slurry was then filtered, and the precipitate was washed with a minimum amount of cold Et2O to give the compound as a white powder.

Reference： [1]Synlett,2014,vol. 25,p. 2644 - 2648
[2]Synlett,2014,vol. 25

47
[ 459-47-2 ]
[ 824-75-9 ]

Yield	Reaction Conditions	Operation in experiment
89%	With tert.-butylhydroperoxide; ammonia; iodine; In water; at 100℃; for 3h;Sealed tube; Green chemistry;	General procedure: A sealed tube equipped with a magnetic stirring bar was charged with ethylarene (1, 1.0 mmol), aq NH3 (2, 25% aq solution,10.0 mmol), I2 (1.1 mmol), and TBHP (6.0 mmol, 70% aq solution) at r.t. The resulting mixture was heated to 100 C for 3.0 h. After completion of the reaction (monitored by TLC), sat.Na2S2O3 solution (10 mL) was added to the reaction mixture,and it was extracted with EtOAc (2 × 20 mL). The organic layer was washed with brine solution (20 mL), dried over anhydrous Na2SO4 and concentrated under reduced pressure. The residue was purified by column chromatography on 100-200 mesh silica gel using EtOAc-n-hexane (1:2) as the eluent to obtain the corresponding benzamide 3.

Reference： [1]Synlett,2015,vol. 26,p. 1677 - 1682

48
[ 61117-58-6 ]
[ 460-00-4 ]
[ 824-75-9 ]

Yield	Reaction Conditions	Operation in experiment
85%	With 1H-imidazole; 1,1'-bis-(diphenylphosphino)ferrocene; palladium diacetate; ammonium chloride; N-ethyl-N,N-diisopropylamine In 1,4-dioxane at 90℃; for 3h; Sealed tube;	General procedure for the synthesis of primary amides: General procedure: To a stirred solution of aryl halide (Br/I) (1 mmol) in dry dioxane in a 25 mL sealed tube, was added Pd(OAc)2 (5 mol%), dppf (6 mol %), DIPEA (2 mmol), imidazole (0.25 mmol), ammonium chloride (2 mmol) and then Co2(CO)8 (0.3 mmol). The seal tube was closed immediately and stirred at 90 °C for 3h. After the reaction time the reaction mixture was cooled to room temperature. The reaction mixture was filtered through celite pad and washed with dioxane, the filtrate was concentrated under reduced pressure and the residue obtained was purified by column chromatography.

Reference： [1]Suresh; Baburajan, Poongavanam; Ahmed, Mansur [Tetrahedron Letters, 2015, vol. 56, # 34, p. 4864 - 4867]

49
[ 61117-58-6 ]
[ 352-34-1 ]
[ 824-75-9 ]

Yield	Reaction Conditions	Operation in experiment
80%	With 1H-imidazole; 1,1'-bis-(diphenylphosphino)ferrocene; palladium diacetate; ammonium chloride; N-ethyl-N,N-diisopropylamine In 1,4-dioxane at 90℃; for 3h; Sealed tube;	General procedure for the synthesis of primary amides: General procedure: To a stirred solution of aryl halide (Br/I) (1 mmol) in dry dioxane in a 25 mL sealed tube, was added Pd(OAc)2 (5 mol%), dppf (6 mol %), DIPEA (2 mmol), imidazole (0.25 mmol), ammonium chloride (2 mmol) and then Co2(CO)8 (0.3 mmol). The seal tube was closed immediately and stirred at 90 °C for 3h. After the reaction time the reaction mixture was cooled to room temperature. The reaction mixture was filtered through celite pad and washed with dioxane, the filtrate was concentrated under reduced pressure and the residue obtained was purified by column chromatography.

Reference： [1]Suresh; Baburajan, Poongavanam; Ahmed, Mansur [Tetrahedron Letters, 2015, vol. 56, # 34, p. 4864 - 4867]

50
[ 824-75-9 ]
[ 882-33-7 ]
4-fluoro-N-(phenylthio)benzamide [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
52%	Stage #1: p-fluorobenzamide With sodium hydride In tetrahydrofuran; mineral oil at 20℃; for 1h; Stage #2: diphenyldisulfane In tetrahydrofuran; mineral oil at 20℃; for 36h;	Typical experimental procedure for NaH-promotedsulfenylation of benzamides with disulfide General procedure: The benzamide (0.2 mmol), NaH (3 equivalents) and dry THF(3 mL) were added to a two-neck flask in turn and stirred atroom temperature for 1 h. Then disulfide (1.5 equivalent) wasadded into the mixture and stirred for another 36 h at roomtemperature. During the whole reaction process, the systemwas kept turbid because of the difficult solubility of NaH inTHF. Then the resulting mixture was filtered and washed withEtOAc to give the solvent, which was concentrated in vacuoand the residue was purified by flash column chromatographyon a silica gel to give the desired product

Reference： [1]Zhang, Xing-Song; Zhang, Xiao-Hong [Phosphorus, Sulfur and Silicon and the Related Elements, 2016, vol. 191, # 1, p. 89 - 94]

51
[ 824-75-9 ]
1,3-diphenylpropene [ No CAS ]
N-[(2E)-1,3-diphenyl-2-propen-1-yl]-4-fluorobenzamide [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
70%	With oxygen; 2,3-dicyano-5,6-dichloro-p-benzoquinone; dibenzoyl peroxide In nitromethane at 100℃; for 24h;	Oxidative coupling reaction of 1,3-diarylpropenes 1; general procedure General procedure: DDQ (20 mol%, 9.08 mg, 0.04 mmol) and BPO (20 mol%,9.69 mg, 0.04 mmol) were added to a mixture of 1,3-diarylpropene1 (0.24 mmol) and substrate 2 (0.2 mmol) in CH3NO2 (1 mL). Thereaction was carried out at 100 °C under an oxygen atmosphere(oxygen balloon) for 24 h. The resulting mixture was purified by flashcolumn chromatography on silica gel (petroleum ether:ethyl acetate =10:1-20:1) to give the desired pure product 3a-k.

Reference： [1]Cheng, Dongping; Zhou, Xiayi; Yuan, Kun; Yan, Jizhong [Journal of Chemical Research, 2016, vol. 40, # 3, p. 127 - 129]

52
[ 127-19-5 ]
[ 824-75-9 ]
N,N’-methylenebis(4-fluorobenzamide) [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
43%	With sodium persulfate; ammonium cerium (IV) nitrate In water at 110℃; for 12h; Schlenk technique; Sealed tube;	8 Example eight In a Schlenk tube charged sequentially on fluorobenzamide (0.5mmol), sodium persulfate (2mmol), ceric ammonium nitrate (0.025mmol), N, N- dimethylacetamide (2mmol), was added 1ml of deionized water, and then the system was sealed and heated in an oil bath at 110 deg.] C for about 12 hours, after the reaction was cooled and extracted with ethyl acetate (15ml × 3), and concentrated by a simple column chromatography (eluent petroleum ether: ethyl acetate = 2: 1) to obtain methylene bis of fluorobenzamide a yield of 43%

Reference： [1]Current Patent Assignee: SUZHOU PERFECT NEW MATERIAL TECHNOLOGY - CN104447391, 2016, B Location in patent: Paragraph 0042; 0043; 0044

53
[ 824-75-9 ]
[ 1131912-76-9 ]
C₁₂H₁₄FNO₂ [ No CAS ]

Reference： [1]Chemistry - A European Journal,2016,vol. 22,p. 15654 - 15658

54
[ 824-75-9 ]
[ 345-89-1 ]

Reference： [1]Organic Letters,2016,vol. 18,p. 5872 - 5875

55
[ 824-75-9 ]
[ 24424-99-5 ]
N,N-di-Boc-4-fluorobenzamide [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
94%	With dmap In neat (no solvent) for 2h; Milling; chemoselective reaction;	General procedure for N-tert-butoxycarbonylation of amides General procedure: To a stainless steel milling jar (50 mL) equipped with stainless steel milling balls (7.0-10.0 mm in diameter) were added amide (1 or 3, 1.0 mmol, 1.0 equiv.), Boc2O (1.2-4.0 mmol, 1.2-4.0 equiv.) and DMAP (6.1-36.6 mg, 0.05-0.30 mmol). The milling jar was clamped into planetary ball mill and milled at 30 Hz for given time. The operation cycle was 60 min on, 10 min off to take sample for TLC. After the elapsed time, the reaction mixture was transferred from the milling jar into a flask with aid of CH2Cl2 (3 x 5 mL)and then was concentrated by rotavapor to afford the crude product, which was purified by flash column chromatography on silica gel using a gradient of ethyl acetate in petroleum ether.
88%	With dmap In acetonitrile at 20℃; for 15h; Inert atmosphere; Sealed tube;
73.1%	With dmap In dichloromethane at 0 - 23℃; Inert atmosphere;

73%	With dmap In dichloromethane at 0 - 20℃; Inert atmosphere;
73%	With dmap In dichloromethane at 0 - 20℃; Inert atmosphere;
	With dmap In dichloromethane at 0 - 23℃; Inert atmosphere;
	With dmap In dichloromethane at 0 - 20℃; Inert atmosphere;	General procedure for N,N-Boc2-amide synthesis. General procedure: A previously published procedure was followed. An oven-dried round-bottomed flask (100 mL) equipped with a stir bar was charged with the primary amide (8.26 mmol, 1.0 equiv.), 4-dimethylaminopyridine (DMAP) (typically, 0.10 equiv.),and dichloromethane (typically, 25 mL), placed under a positive pressure of nitrogen, and subjected to three evacuation/backfilling cycles under high vacuum.84 Di-tert-butyl dicarbonate (typically, 2.0 equiv.) was added portion-wise to the reaction mixture with vigorous stirring at 0 °C, and the reaction mixture was stirred overnight at room temperature. After the indicated time, the reaction mixture was concentrated and unless stated otherwise, purified directly by chromatography on silica gel (hexanes/ethyl acetate) to give analytically pure product.

Reference： [1]Shi, Weijia; Sun, Guoping; Zou, Gang [Tetrahedron Letters, 2020, vol. 61, # 29]
[2]Luo, Zhongfeng; Wu, Hongxiang; Li, Yue; Chen, Yuwen; Nie, Jingyi; Lu, Siqi; Zhu, Yulin; Zeng, Zhuo [Advanced Synthesis and Catalysis, 2019, vol. 361, # 17, p. 4117 - 4125]
[3]Shi, Shicheng; Szostak, Michal [Organic Letters, 2016, vol. 18, # 22, p. 5872 - 5875]
[4]Meng, Guangrong; Shi, Shicheng; Lalancette, Roger; Szostak, Roman; Szostak, Michal [Journal of the American Chemical Society, 2018, vol. 140, # 2, p. 727 - 734]
[5]Sureshbabu, Popuri; Azeez, Sadaf; Muniyappan, Nalluchamy; Sabiah, Shahulhameed; Kandasamy, Jeyakumar [Journal of Organic Chemistry, 2019, vol. 84, # 18, p. 11823 - 11838]
[6]Lei, Peng; Meng, Guangrong; Ling, Yun; An, Jie; Nolan, Steven P.; Szostak, Michal [Organic Letters, 2017, vol. 19, # 24, p. 6510 - 6513]
[7]Tao, Jiasi; Yu, Weijie; Luo, Jin; Wang, Tao; Ge, Wanling; Zhang, Ziwei; Yang, Bingjie; Xiong, Fei [Journal of Chemical Research, 2019, vol. 43, # 11-12, p. 486 - 492]

56
[ 824-75-9 ]
2,10-difluoro-5H-dibenzo[c,e]azepine-5,7(6H)-dione [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
80%	With potassium sulfite; bis(acetylacetonato)palladium(II); trifluoroacetic acid at 30℃; for 24h; Inert atmosphere; Schlenk technique;	5 Synthesis of 10-difluoro-5H-dibenzo [c, e] azepine-5,7 (6H) -dione A solution of p-fluorobenzamide (139 mg, 1 mmol), palladium acetylacetonate (24.4 mg, 0.08 mmol) and potassium sulfite (242.4 mg, 2 mmol) were successively added to a Schlenk reaction flask, In the atmosphere, 2 mL of trifluoroacetic acid was added and reacted at 30 ° C for 24 hours. After the completion of the reaction, the solvent was removed under reduced pressure and the column was separated by column chromatography (eluent: petroleum ether: ethyl acetate = 5: 1, V: V) The main product of white solid was 207.2 mg, yield 80%
40%	With sodium persulfate; palladium diacetate In trifluoroacetic acid at 130℃; for 24h;

Reference： [1]Current Patent Assignee: DALIAN UNIVERSITY OF TECHNOLOGY - CN106699661, 2017, A Location in patent: Paragraph 0044 - 0046
[2]Kondapalli, Vijayakumar; Yu, Xiaoqiang; Yamamoto, Yoshinori; Bao, Ming [Journal of Organic Chemistry, 2017, vol. 82, # 4, p. 2288 - 2293]

57
[ 459-22-3 ]
[ 824-75-9 ]

Yield	Reaction Conditions	Operation in experiment
81%	With copper(I) oxide; oxygen; ammonium chloride; sodium hydroxide In acetonitrile at 120℃; for 30h; Schlenk technique;
56%	With tert.-butylhydroperoxide; ammonium hydroxide; iodine In acetonitrile at 70℃; for 36h; Sealed tube;

Reference： [1]Chen, Xiuling; Peng, Yanhong; Li, Yan; Wu, Minghu; Guo, Haibing; Wang, Jian; Sun, Shaofa [RSC Advances, 2017, vol. 7, # 30, p. 18588 - 18591]
[2]Nageswara Rao, Sadu; Reddy, N. Naresh Kumar; Samanta, Supravat; Adimurthy, Subbarayappa [Journal of Organic Chemistry, 2017, vol. 82, # 24, p. 13632 - 13642]

58
[ 824-75-9 ]
[ 4637-24-5 ]
3-(4-fluorophenyl)-1H-1,2,4-triazole [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
78.8%	Stage #1: p-fluorobenzamide; <i>N</i>,<i>N</i>-dimethyl-formamide dimethyl acetal at 120℃; for 2h; Stage #2: With hydrazine hydrate; acetic acid In water at 90℃; for 2h;	5 5.4.4. General procedure for preparation of triazole intermediates(19a-19f) General procedure: A mixture of different amides A1-A6 (8.1 mmol) and DMF-DMA(10 mL, 0.08 mol) was stirred at 120 C for 2 h.The mixture was concentrated under reduced pressure to afford white solid, which was dissolved in HOAc (10 mL), and then 80% hydrazine hydrate(0.61 g, 9.8 mmol) was drop-wise to the solution. The mixture was stirred at 90 C for 2 h. The solvent was removed in vacuo and the mixture was added in ether at 0 C for 30 min. The precipitate was filtered and dried under reduced pressure to afford 19a-19f as white solid.

Reference： [1]Sun, Xiaoqing; Hong, Zexin; Liu, Moyi; Guo, Su; Yang, Di; Wang, Yong; Lan, Tian; Gao, Linyu; Qi, Hongxia; Gong, Ping; Liu, Yajing [Bioorganic and Medicinal Chemistry, 2017, vol. 25, # 10, p. 2800 - 2810]

59
[ 67-56-1 ]
[ 824-75-9 ]
[ 3424-93-9 ]

Yield	Reaction Conditions	Operation in experiment
56%	With potassium hydroxide In dimethyl sulfoxide at 20℃; for 16h;	3.5 4.2. Typical procedure for the synthesis of 2aa General procedure: A mixture of 2-fluorobenzamide (1a, 69.5 mg, 0.5 mmol), MeOH (ca. 32.0 mg, 1.0 mmol), KOH (56.0 mg, 1.0 mmol) and DMSO (2.0 mL) in a 25 mL screw-capped thick-walled Pyrex tube was stirred at room temperature for 16 h, and then water (10 mL) was added to the reaction mixture with stirring, and the mixture was extracted with ethyl acetate three times (3 * 10 mL). The combined organic phases were dried over Na2SO4 overnight. The filtered solution was concentrated under reduced pressure, and the crude residue was purified by column chromatography on silica gel with the use of petroleum ether/ethyl acetate/trimethylamine (gradient mixture ratio from 6:1:0.05 to 2:1:0.05 in volume) to afford 2aa as a white solid in 80% yield (60.7 mg).

Reference： [1]Su, Ji; Chen, Qian; Lu, Le; Ma, Yuan; Auyoung, George Hong Lok; Hua, Ruimao [Tetrahedron, 2018, vol. 74, # 2, p. 303 - 307]

60
[ 824-75-9 ]
[ 232951-83-6 ]
tert-butyl 2-(4-fluorobenzamido)nicotinate [ No CAS ]

Reference： [1]ACS Catalysis,2018,vol. 8,p. 203 - 218

61
[ 824-75-9 ]
[ 615-41-8 ]
[ 838-55-1 ]

Yield	Reaction Conditions	Operation in experiment
88%	With potassium carbonate; N,N`-dimethylethylenediamine; In toluene; at 110℃; for 48h;Schlenk technique; Inert atmosphere;	General procedure: An oven-dried Schlenk tube was charged with benzamide 1 (0.5 mmol), K2CO3 (207 mg, 1.5 mmol) and aryl iodide 2 (1.0 mol). The tube was evacuated and backfilled with N2 (3 ×), and then DMEDA (0.2 mmol) and anhyd toluene (5.0 mL) were added. The reaction mixture was stirred at 110 C for 48 h. H2O was added and the crude product was extracted with EtOAc. The combined organic phases were washed with brine and H2O, dried (Na2SO4), and concentrated under reduced pressure. The product was purified by silica gel chromatographyto give the desired N-arylated benzamides (Table 2).

Reference： [1]Synthesis,2018,vol. 50,p. 1090 - 1096

62
[ 824-75-9 ]
[ 625-99-0 ]
4-fluoro-N-(3-chlorophenyl)benzamide [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
73%	With potassium carbonate; N,N`-dimethylethylenediamine In toluene at 110℃; for 48h; Schlenk technique; Inert atmosphere;	N-Arylated Benzamides 3 General procedure: An oven-dried Schlenk tube was charged with benzamide 1 (0.5 mmol), K2CO3 (207 mg, 1.5 mmol) and aryl iodide 2 (1.0 mol). The tube was evacuated and backfilled with N2 (3 ×), and then DMEDA (0.2 mmol) and anhyd toluene (5.0 mL) were added. The reaction mixture was stirred at 110 ° C for 48 h. H2O was added and the crude product was extracted with EtOAc. The combined organic phases were washed with brine and H2O, dried (Na2SO4), and concentrated under reduced pressure. The product was purified by silica gel chromatographyto give the desired N-arylated benzamides (Table 2).

Reference： [1]Huang, Fei; Wu, San; Hu, Weiye; Zhang, Songlin [Synthesis, 2018, vol. 50, # 5, p. 1090 - 1096]

63
[ 824-75-9 ]
[ 71838-16-9 ]
2-(4-fluorophenyl)-6-methylbenzo[d]oxazole [ No CAS ]

Reference： [1]RSC Advances,2018,vol. 8,p. 2267 - 2270

64
[ 824-75-9 ]
[ 583-04-0 ]
C₁₀H₁₀FNO [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
64%	With iron(III) chloride; silver hexafluoroantimonate; bis[dichloro(pentamethylcyclopentadienyl)ruthenium(III)]; tri-tert-butylphosphonium tetrafluoroborate In 1,2-dichloro-ethane at 100℃; for 16h; Inert atmosphere;	4 Specific Example 4: 4-fluorobenzamide and allyl benzoate; 55.7 mg (0.4 mmol) of 4-fluorobenzamide, 32.4 mg (0.2 mmol) of allyl benzoate, 6.2 mg (0.01 mmol) of dichloro(pentamethylcyclopentadienyl) ruthenium (III) Polymer, 13.8 mg (0.04 mmol) of silver hexafluoroantimonate, 11.3 mg (0.1 mmol) of ferric fluoride, 5.8 mg (0.02 mmol) of tri-tert-butylphosphonium tetrafluoroborate were added to the reaction tube, and 2 mL 1 was added. 1,2-dichloroethane, under nitrogen atmosphere, 100 °C for 16 hours after the reaction was cooled, filtered and the filtrate rotary evaporated to remove the solvent, the residue was purified by silica gel column chromatography, petroleum ether - ethylacetate, The mixture was subjected to TLC, and the product-containing effluent was combined. The solvent was evaporated on a rotary evaporator and dried in vacuo to give 4-fluoro-2- allylbenzamide as a white solid. Yield: 64 %

Reference： [1]Current Patent Assignee: WENZHOU UNIVERSITY - CN108129340, 2018, A Location in patent: Paragraph 0027

65
[ 824-75-9 ]
tert-butyl (4-(5-chloro-2-fluoropyridin-4-yl)thiazol-2-yl)((tetrahydro-2H-pyran-4-yl)methyl)carbamate [ No CAS ]
N-(5-chloro-4-(2-(((tetrahydro-2H-pyran-4-yl)methyl)amino)thiazol-4-yl)pyridin-2-yl)-4-fluorobenzamide [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
8%	With sodium hydride In dimethyl sulfoxide at 100 - 110℃; for 48h; Inert atmosphere;	4.1.2 4-(5-Chloro-2-fluoropyridin-4-yl)-N-((tetrahydro-2H-pyran-4-yl)methyl)thiazol-2-amine (12) and 4-(5-chloro-2-((2-methoxyethyl)amino)pyridin-4-yl)-N-((tetrahydro-2H-pyran-4-yl)methyl)thiazol-2-amine (13) General procedure: 53l (0.3g, 0.71mmol), 2-methoxyethan-1-amine (0.16g, 2.1mmol) and DIEA (0.36g, 2.8mmol) were dissolved in DMSO (10mL) under N2 protection and the reaction mixture was stirred at 100-110°C for two days. The resulting mixture was poured into cold water and extracted with ethyl acetate (3×20mL) and washed with water (3×20mL) and brine (20mL). The combined organic layers were dried over anhydrous Na2SO4 and evaporated to dryness. The crude product was purified by silica gel flash chromatography (eluting with ethyl acetate in petroleum ether 2-5%) to give 12 (53mg, yield=23%) and 13 (0.33g, yield=43%) as white solid.
3.1%	Stage #1: p-fluorobenzamide With sodium hydride In N,N-dimethyl-formamide at 20℃; for 0.166667h; Stage #2: tert-butyl (4-(5-chloro-2-fluoropyridin-4-yl)thiazol-2-yl)((tetrahydro-2H-pyran-4-yl)methyl)carbamate In N,N-dimethyl-formamide at 55℃; for 4h;	8 Example 8: synthesis of N-(5-chloro-4-(2-(((tetrahydro-2H-pyran-4-yl) methyl)amino)thiazol-4-yl)pyridin-2-yl)-4-fluorobenzamide 4-fluorobenzamide (0.65 g, 4.68 mmol) was dissolved in N, N-dimethylformamide DMF (15 mL), and NaH (0.19g, 4.68mmol) was added at room temperature. The reaction solution was stirred at room temperature for 10 min, and then tert-butyl (4-(5-chloro-2-fluoropyridin-4-yl)thiazol-2-yl((tetrahydro-2H-pyran-4-yl)methyl)carbam ate (1g, 2.34 mmol) was added. The reaction solution was warmed up to 55 °C and reacted for 4 h. The reaction was monitored by TLC. The reaction was stopped, and then the reaction solution was poured into water, and extracted with EA (3 × 20 mL). The organic phase was washed with saturated brine, dried over sodium sulfate, filtered, and concentrated to give a crude. The crude was isolated by thick preparation plate (PE:EA=1:1) to give 0.032 g of N-(5-chloro-4-(2-(((tetrahydro-2H-pyran-4-yl)methyl)amino)thiazol-4-yl)pyridin-2-yl)-4-fluorobenzamide as a white solid, yield 3.1%, 1H NMR (400MHz, CDCl3) δ 8.96 (s, 1H), 8.52 (s, 1H), 8.30 (s, 1H), 7.93-7.96 (m, 2H), 7.41 (s, 1H), 7.19 (t, J=8.4Hz, 2H), 5.35-5.38 (m, 1H), 4.00-4.04 (m, 2H), 3.40-3.50 (m, 2H), 3.24 (t, J=6.4Hz, 2H), 1.95-2.01 (m, 1H), 1.72-1.76 (m, 2H), 1.36-1.45 (m, 2H). (ESI+): m/z 447.1 [M+H]+.

Reference： [1]Wang, Beilei; Wu, Jiaxin; Wu, Yun; Chen, Cheng; Zou, Fengming; Wang, Aoli; Wu, Hong; Hu, Zhenquan; Jiang, Zongru; Liu, Qingwang; Wang, Wei; Zhang, Yicong; Liu, Feiyang; Zhao, Ming; Hu, Jie; Huang, Tao; Ge, Juan; Wang, Li; Ren, Tao; Wang, Yuxin; Liu, Jing; Liu, Qingsong [European Journal of Medicinal Chemistry, 2018, vol. 158, p. 896 - 916]
[2]Current Patent Assignee: SHANGHAI JIONGSHUO PHARMACEUTICAL TECHNOLOGY; GENFLEET THERAPEUTICS SHANGHAI - EP3613737, 2020, A1 Location in patent: Paragraph 0084-0085

66
[ 7188-38-7 ]
[ 824-75-9 ]
(E)-N-(N,N'-di-tert-butylcarbamimidoyl)-4-fluorobenzamide [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
83%	With caesium carbonate; palladium dichloride In acetonitrile at 70℃; for 2h;	General procedure: To a round bottom flask was added amides 1 (0.3 mmol), tert-butyl isocyanide 2 (0.72 mmol),PdCl2, and Cs2CO3. And MeCN (2.0 mL) was added under air. The reaction mixture was stirred at 70°C about 2 h, and the reaction progress monitored by TLC. The reaction mixture was removedunder vacuum, and then the residue was further purified by silica gel column chromatography(petroleum ether and ethyl acetate) to afford the products 3.

Reference： [1]Li, Pei-Xia; Meng, Xiu-Jin; Yang, Li; Tang, Hai-Tao; Pan, Ying-Ming [Synlett, 2018, vol. 29, # 17, p. 2326 - 2330]

67
[ 459-56-3 ]
[ 824-75-9 ]
4-fluoro-N-(4-fluorobenzoyl)benzamidium hydroxide [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
53%	With sodium hypochlorite; sodium iodide In methanol; water; acetonitrile at 80℃; for 8h; Inert atmosphere;	Benzamide derivatives were synthesized according to the developed earlier method [2] with minor modifications (Scheme 1). A mixture of NaI (2 mmol) and a substituted amide (1.5 mmol) was added to amixture of solvents (CH3OH/CH3CN 20 mL), and subsequently substituted benzyl alcohols (1 mmol) and NaOCl (8 mmol, 70 wt % in H2O) were added under the atmosphere of argon. The reaction mixture was stirred for ca 8 h at 80 °C. The progress of the reaction was monitored by TLC. After completion, the reaction mixture was cooled to room temperature and poured into crushed ice. The corresponding precipitated product was filtered off and recrystallized from asuitable solvent(s). The colorless crystals of 2 wereobtained after re-crystallization from acetone. 4-Fluoro-N-(4-fluorobenzoyl)benzamidium hydroxide(1). Yield 53 %, mp 137 °C. FT-IR spectrum, ν,cm-1: 33175 (N-H), 1729 (C=O), 1670 (C=Carom ). 1HNMR spectrum, δ, ppm: 7.85-7.96 m (C6H4), 8.78 s (NH). 13C NMR spectrum, δ, ppm: 128.7-169.2 (C-Ar), 183.7 (C=O). Found, %: C 60.26; H 3.92; N 5.01.C14H11F2NO3. Calculated, %: C 60.22; H 3.97; N 5.02.

Reference： [1]Raheel; Imtiaz-ud-Din; Taj; Tahir; Al-Shakban [Russian Journal of General Chemistry, 2018, vol. 88, # 7, p. 1508 - 1514]

68
[ 824-75-9 ]
[ 1006-40-2 ]

Yield	Reaction Conditions	Operation in experiment
60%	With N-Bromosuccinimide; palladium diacetate; trifluoroacetic acid; In 1,2-dichloro-ethane; at 60℃; for 24h;Sealed tube;	General procedure: To a clean oven-dried 15 mL sealed tube equipped with magnetic stir bar, benzamide (0.25 mmol, 1.0 equiv), Pd(OAc)2 (5.0 mol%, 2.8 mg), and NXS (0.3 mmol, 1.2 equiv.) were added sequentially. DCE (2.0 mL) was then added to the reaction mixture followed by trifluoroacetic acid (475 muL). The tube was tightly closed and placed in a preheated oil bath of 60 C and stirred for 24 h. In each case, the reaction was monitored by TLC, and after completion, the reaction mixture was cooled to room temperature. The solvent was evaporated under reduced pressure and then diluted with ethyl acetate followed by neutralization with a saturated solution of sodium bicarbonate. After extraction with ethyl acetate (15 mL×3), the organic layer was washed with brine solution and dried over sodium sulphate. After evaporation of the solvent, the crude mixture was purified by column chromatography silica gel using ethyl acetate/hexanes as the eluent.

Reference： [1]New Journal of Chemistry,2019,vol. 43,p. 3462 - 3468
[2]Catalysis Communications,2019,vol. 131

69
[ 824-75-9 ]
[ 659-41-6 ]

Yield	Reaction Conditions	Operation in experiment
80%	Stage #1: 4-fluoro-benzamide With triethyl borane; phenylsilane; anhydrous potassium acetate In tetrahydrofuran; tert-butyl methyl ether at 120℃; Inert atmosphere; Schlenk technique; Sealed tube; Stage #2: With hydrogenchloride In ethyl acetate at 20℃; for 8h; Inert atmosphere; chemoselective reaction;
80%	Stage #1: 4-fluoro-benzamide With triethyl borane; phenylsilane; anhydrous potassium acetate In tert-butyl methyl ether at 120℃; Inert atmosphere; Glovebox; Schlenk technique; Sealed tube; Stage #2: With hydrogenchloride In ethyl acetate at 20℃; for 8h; Inert atmosphere; Schlenk technique; Glovebox; Sealed tube;
69%	Stage #1: 4-fluoro-benzamide With bis(tetrahydrofuran)calcium di(bis(trimethylsilyl)amide); 4,4,5,5-tetramethyl-1,3,2-dioxaborolane In toluene at 120℃; for 36h; Inert atmosphere; Schlenk technique; Stage #2: With hydrogenchloride In diethyl ether; toluene Inert atmosphere; Schlenk technique;

64%	Stage #1: 4-fluoro-benzamide With phenylsilane; C₂₈H₁₈ClMnN₂O₂; potassium-t-butoxide In tetrahydrofuran at 50℃; for 12h; Inert atmosphere; Glovebox; Stage #2: With sodium hydroxide In tetrahydrofuran for 3h; Inert atmosphere; Glovebox; Stage #3: With hydrogenchloride In methanol; diethyl ether Glovebox; Inert atmosphere;
	Multi-step reaction with 2 steps 1: La(CH₂C₆H₄NMe₂-o)₃ on SBA-15 / toluene / 24 h / 120 °C / Schlenk technique; Inert atmosphere 2: hydrogenchloride / ethyl acetate; diethyl ether / 20 °C / Schlenk technique; Inert atmosphere
	Multi-step reaction with 2 steps 1: 4,4,5,5-tetramethyl-1,3,2-dioxaborolane / neat (no solvent) / 24 h / 120 °C / Inert atmosphere; Sealed tube 2: hydrogenchloride / ethyl acetate; diethyl ether / 1 h / 20 °C
	Stage #1: 4-fluoro-benzamide With Fe(CO)<SUB>4</SUB>(1,3-bis (2,4,6-trimethylphenyl)imidazol-2-ylidene); phenylsilane; Zinc di(trifluoromethanesulphonate) In cyclohexane at 110℃; for 20h; Schlenk technique; Inert atmosphere; Irradiation; Stage #2: With hydrogenchloride In 1,4-dioxane Schlenk technique; Inert atmosphere; Irradiation; chemoselective reaction;

Reference： [1]Yao, Wubing; Fang, Huaquan; He, Qiaoxing; Peng, Dongjie; Liu, Guixia; Huang, Zheng [Journal of Organic Chemistry, 2019]
[2]Yao, Wubing; Fang, Huaquan; He, Qiaoxing; Peng, Dongjie; Liu, Guixia; Huang, Zheng [Journal of Organic Chemistry, 2019, vol. 84, # 10, p. 6084 - 6093]
[3]Gong, Mingliang; Guo, Chenjun; Jiang, Linhong; Luo, Yunjie; Yu, Chong [Organometallics, 2021, vol. 40, # 9, p. 1201 - 1206]
[4]Das, Hari S.; Das, Shyamal; Dey, Kartick; Singh, Bhagat; Haridasan, Rahul; Das, Arpan; Ahmed, Jasimuddin; Mandal, Swadhin K. [Chemical Communications, 2019, vol. 55, # 79, p. 11868 - 11871]
[5]Guo, Chenjun; Zhang, Fangcao; Yu, Chong; Luo, Yunjie [Inorganic Chemistry, 2021, vol. 60, # 17, p. 13122 - 13135]
[6]Yi, Jaeeun; Kim, Hyun Tae; Jaladi, Ashok Kumar; An, Duk Keun [Bulletin of the Korean Chemical Society, 2022, vol. 43, # 1, p. 129 - 132]
[7]Wu, Jiajun; Darcel, Christophe [ChemCatChem, 2022, vol. 14, # 9]

70
[ 17830-03-4 ]
[ 824-75-9 ]
C₉H₁₆B₁₀FNO [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	With potassium phosphate; tris-(dibenzylideneacetone)dipalladium⁽⁰⁾; DavePhos In toluene at 100℃; Inert atmosphere;
	With potassium phosphate; tris-(dibenzylideneacetone)dipalladium⁽⁰⁾; DavePhos In toluene at 100℃; for 2h; Inert atmosphere;
	With potassium phosphate; tris-(dibenzylideneacetone)dipalladium⁽⁰⁾; DavePhos In toluene at 100℃; Inert atmosphere;	1. General procedure for synthesis of 1a-1k(Take 1a as an example) General procedure: To a 25 mL dried flask was sequentially added 9-iodo-o-carborane (500 mg, 1.85mmol), 3 equivalents of benzamide (671.5 mg, 5.54 mmol ), 5 equivalents of K3PO4(1.96 g, 9.23 mmol), 5 mol % of 2-dicyclohexylphosphino-2’-(N, N-dimethylamino)biphenyl (DavePhos) (36 mg, 0.09 mmol), 2.5 mol % of Pd2(dba)3 (42 mg,0.046 mmol) and 8 mL of toluene under argon atmosphere. After the reaction mixturewas stirred at 100 oC for 2-4 hours until the color was changed from purple to orange,the reaction mixture was cooled to room temperature. Then, the mixture was filteredthrough a short silica gel column using ethyl acetate as eluent. After evaporation ofthe solvent, the residue was purified by column chromatography on 200-300 meshsilica gel with petroleum ether/EtOAc=4:1 as eluent, and gave 1a with 55% yield(267 mg).

Reference： [1]Zhang, Cai-Yan; Cao, Ke; Xu, Tao-Tao; Wu, Ji; Jiang, Linhai; Yang, Junxiao [Chemical Communications, 2019, vol. 55, # 6, p. 830 - 833]
[2]Wu, Ji; Cao, Ke; Zhang, Cai-Yan; Xu, Tao-Tao; Ding, Li-Fang; Li, Bo; Yang, Junxiao [Organic Letters, 2019, vol. 21, # 15, p. 5986 - 5989]
[3]Cao, Ke; Zhang, Cai-Yan; Xu, Tao-Tao; Wu, Ji; Ding, Li-Fang; Jiang, Linhai; Yang, Junxiao [Journal of Organometallic Chemistry, 2019, vol. 902]

71
[ 824-75-9 ]
(R)-2-(5-bromobenzo[b]thiophen-3-yl)-2-((R)-1,1-dimethylethylsulfinylamino)-N-(4-methoxybenzyl)-N-methylpropane-1-sulfonamide [ No CAS ]
(R)-N-(3-(2-amino-1-(N-(4-methoxybenzyl)-N-methylsulfamoyl)propan-2-yl)benzo[b]thiophene-5-yl)-4-fluorobenzamide [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
90.3%	With copper(l) iodide; (R,R)-N,N'-dimethyl-1,2-diaminocyclohexane; potassium carbonate In toluene at 100℃; for 12h; Inert atmosphere;	1.4 Step 4) (R)-N-(3-(2-amino-1-(N-(4-methoxybenzyl))-N-methylsulfamoyl)propan-2-yl)benzo[b]thiophen-5-yl)-4-fluorobenzamide synthesis (R)-2-(5-bromobenzo[b]thiophen-3-yl)-2-((R)-1,1-dimethylethylsulfinylamino)-N-(4-methoxybenzyl)-N-methylpropane-1-sulfonamide (500 mg, 0.85 mmol), 4-fluorobenzamide (177 mg, 1.27 mmol), potassium carbonate (294 mg, 2.13 mmol), cuprous iodide (162 mg, 0.85 mmol), (1R, 2R)-N1,N2-dimethylcyclohexane-1,2-diamine (242 mg, 1.70 mmol) and toluene (3 mL) were added to a 50 mL single-necked flask. The reaction was continued at 100 ° C for 12 hours under nitrogen protection; the reaction was stopped. Water (20 mL) was added, and then extracted with dichloromethane (30 mL×2). The organic phase was collected, dried over anhydrous sodium sulfate (1.5 g), filtered, the title compound was obtained as a pale yellow oil (416 mg, 90%).

Reference： [1]Current Patent Assignee: SHENZHEN DONGYANGGUANG INDUSTRIAL DEVELOPMENT CO LTD - CN109796447, 2019, A Location in patent: Paragraph 0201; 0213; 0214; 0215; 0216

72
[ 824-75-9 ]
(4-fluorobenzoyl)sulfamoyl fluoride [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
98%	With fluorosulfonyl fluoride; 1,8-diazabicyclo[5.4.0]undec-7-ene; In dimethyl sulfoxide; at 50℃; for 18h;	General procedure: A mixture of amides 1 (1 mmol, 1 eq.), DBU (5 mmol, 5 equiv, 761.2 mg, 0.75 mL), and DMSO (1 mL) was allowed to stir at 50 C under the atmosphere of a SO2F2 balloon overnight (monitored by TLC until complete consumption of amide starting materials). The reaction mixture was quenched by 2 M HCl (10 mL). Then the reaction mixture was extracted with ethyl acetate (3 × 20 mL) and the extracts were washed with water, and concentrated to dryness under reduced pressure. The residue was purified by column chromatography on silica gel using pure ethyl acetate as eluent to give the desired product (2).

Reference： [1]Beilstein Journal of Organic Chemistry,2019,vol. 15,p. 1907 - 1912

73
[ 824-75-9 ]
2'-chloro-4'-fluorobenzamide [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
68%	With N-chloro-succinimide; palladium diacetate; trifluoroacetic acid at 90℃; for 24h; Sealed tube; regioselective reaction;	2.1. General procedure for palladium(II)-catalyzed ortho-halogenation of benzamides General procedure: To a clean oven-dried 15 mL sealed tube equipped with magnetic stir bar, benzamide (0.25 mmol, 1.0 equiv), Pd(OAc)2 (5.0 mol%, 2.8 mg), and NXS (0.3 mmol, 1.2 equiv.) were added sequentially. DCE (2.0 mL) was then added to the reaction mixture followed by trifluoroacetic acid (475 μL). The tube was tightly closed and placed in a preheated oil bath of 60 °C and stirred for 24 h. In each case, the reaction was monitored by TLC, and after completion, the reaction mixture was cooled to room temperature. The solvent was evaporated under reduced pressure and then diluted with ethyl acetate followed by neutralization with a saturated solution of sodium bicarbonate. After extraction with ethyl acetate (15 mL×3), the organic layer was washed with brine solution and dried over sodium sulphate. After evaporation of the solvent, the crude mixture was purified by column chromatography silica gel using ethyl acetate/hexanes as the eluent.

Reference： [1]Jaiswal, Yogesh; Kumar, Amit [Catalysis Communications, 2019, vol. 131]

74
[ 824-75-9 ]
tert-butyl 6-(6-bromopyridine-2-carbonyl)-2-azaspiro[3.3]heptane-2-carboxylate [ No CAS ]
tert-butyl 6-(6-((4-fluorobenzoyl)amino)pyridine-2-carbonyl)-2-azaspiro[3.3]heptane-2-carboxylate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
43.4%	With copper(l) iodide; (R,R)-N,N'-dimethyl-1,2-diaminocyclohexane; potassium carbonate In water; toluene at 90℃; for 12h; Inert atmosphere;	1.3 Step 3) Synthesis of tert-butyl 6-(6-((4-fluorobenzoyl)amino)pyridine-2-carbonyl)-2-azaspiro[3.3]heptane-2-carboxylate Tert-butyl 6-(6-bromopyridine-2-carbonyl)-2-azaspiro[3.3]heptane-2-carboxylate (600 mg, 1.57 mmol), 4-fluorobenzamide (350 mg, 2.51 mmol), potassium carbonate (1.5g, 10.9mmol), cuprous iodide (100mg, 0.52mmol), (1R, 2R)-N1,N2-dimethylcyclohexane-1,2-diamine (135mg, 0.95mmol), water (1.5mL) and toluene (10mL) were added to a 100mL single-necked flask, under nitrogen protection at 90 to continue the reaction for 12 hours; stop the reaction, add water (20mL), and then extracted with dichloromethane (30mL × 2 ), the organic phase was collected, dried over anhydrous sodium sulfate (1.5g), filtered, the filtrate was spin-dried under reduced pressure, and purified by column chromatography (petroleum ether/ethyl acetate (v/v) = 4/1) to obtain the title compound It is a white solid (0.3g, 43.4%).

Reference： [1]Current Patent Assignee: SHENZHEN DONGYANGGUANG INDUSTRIAL DEVELOPMENT CO LTD - CN111187252, 2020, A Location in patent: Paragraph 0215; 0226-0230

75
[ 208121-80-6 ]
[ 824-75-9 ]

Yield	Reaction Conditions	Operation in experiment
91%	With copper dichloride In dimethyl sulfoxide at 120℃; for 11h;	General procedure for CuCl2-promoted oxidative C-N bond cleavage of N-benzoyl aminoacids for primary aryl amides 2. General procedure: A mixture of benzoyl amino acid 1 (0.5 mmol), CuCl2 (85 mg,0.5 mmol), and DMSO (0.5 mL) was placed in a 25 mL flask under air. The tube was heated at120 for 11 h. The reaction mixture was cooled, diluted with ethyl acetate (10 mL), filtered through Celite, and concentrated in vacuo. The residue was purified by silica gel columnchromatography with ethyl acetate/ petroleum ether (ethyl acetate/ petroleum ether = 1:3) toafford the desired product 2.
91%	With copper dichloride In dimethyl sulfoxide at 120℃; for 11h;	General procedure for CuCl2-promoted oxidative C-N bond cleavage of N-benzoyl amino acids for primary aryl amides 2. General procedure: A mixture of benzoyl amino acid 1 (0.5 mmol), CuCl2 (85 mg, 0.5 mmol), and DMSO (0.5 mL) was placed in a 25 mL flask under air. The tube was heated at 120 for 11 h. The reaction mixture was cooled, diluted with ethyl acetate (10 mL), filtered through Celite, and concentrated in vacuo. The residue was purified by silica gel column chromatography with ethyl acetate/ petroleum ether (ethyl acetate/ petroleum ether = 1:3) to afford the desired product 2.

Reference： [1]Chen, Junmin; Liu, Wei; Zhao, Yongli; Zhou, Liandi [ARKIVOC, 2016, vol. 2016, # 6, p. 52 - 62]
[2]Zhou, Liandi; Liu, Wei; Zhao, Yongli; Chen, Junmin [Arkivoc, 2021, vol. 2016, # 6, p. 52 - 62]

76
[ 824-75-9 ]
[ 67-68-5 ]
4-fluoro-N-[(methylthio)methyl]benzamide [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
66%	With acetic acid at 140℃; for 18h; Schlenk technique; Sealed tube; Green chemistry;	N-[(Methylthio)methyl]benzamide (2a); Typical Procedure General procedure: Benzamide (121 mg, 1 mmol) and AcOH (10 mmol) were added to a solution of DMSO (6.0 mL), the mixture was stirred in a sealed Schlenk tube in air at 140 °C for 18 h (TLC monitoring). Once the reaction was completed, the mixture was treated with H2O (15.0 mL) and EtOAc (8.0 mL). The organic and aqueous layers were then separated, and the aqueous layer was extracted with EtOAc (3 x 8 mL). The combined organic extracts were dried (Na2SO4), then the solvent was removed under reduced pressure and the remaining residue was purified by column chromatography to give 2a32 as a white solid; yield: 160.2 mg (88%).

Reference： [1]Chen, Jing; Ma, Yongmin; Zhang, Yi; Zhou, Dongheng [Synthesis, 2020, vol. 52, # 2, p. 297 - 303]

77
[ 824-75-9 ]
[ 723-46-6 ]
[ 68-11-1 ]
4-(2-(4-fluorophenyl)-4-oxothiazolidin-3-yl)-N-(5-methylisoxazol-3-yl)benzenesulfonamide [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
80%	In toluene at 120℃; for 12h;	3.3. Typical Experimental Procedure for the Synthesis of Sulfamethaoxazole Incorporated Substituted4-Thiazolidinone Hybrid (7a) General procedure: The mixture of appropriate 4-amino-N-(5-methylisoxazol-3-yl)benzenesulfonamide (4) (1 mmol),benzaldehydes (5a) (1 mmol) and mercapto acetic acid (6) (1.2 mmol) in toluene (5 mL) was placed in around bottom flask. The mixture was refluxed at 120 °C for an appropriate time until the completionof the reaction. The progress of the reaction was monitored by TLC using ethyl acetate: hexane asa solvent system. The reaction mixture was quenched with crushed ice and extracted with ethylacetate (2 15 mL). The organic extracts were washed with brine solution (2 15 mL) and driedover anhydrous sodium sulphate. The solvent was evaporated under reduced pressure to aord thecorresponding crude compounds. The obtained crude compounds were recrystallized using ethanol .

Reference： [1]Al-Omar, Mohamed A.; Bhat, Mashooq A.; Khan, Azmat Ali; Naglah, Ahmed M. [Molecules, 2020, vol. 25, # 16]

78
[ 824-75-9 ]
[ 3137-63-1 ]
4-fluoro-N-(2-trichloromethylquinazolin-4-yl)benzamide [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
88%	With sodium hydride In N,N-dimethyl-formamide at 0 - 20℃; Inert atmosphere;	3.5. General Procedure for the Preparation of Compounds (2), (5-25) General procedure: To a solution of the appropriate carboxamide compound (1.06 mmol, 1.5 equiv.) in dry DMF (3mL) at 0 °C under N2, 60% sodium hydride in oil (25.5 mg, 1.06 mmol, 1.5 equiv) were added portionwise. The resulting mixture were added dropwise to a solution of 4-chloro-2-(trichloromethyl)quinazoline (4) (200 mg, 0.71 mmol, 1.0 equiv.) in dry DMF (2 mL) at 0 °C under N2.The reaction was stirred overnight at rt. Then, the excess of NaH was hydrolyzed with ice. Thereaction mixture was extracted with EtOAc and washed three times with brine. The organic layerwas dried with Na2SO4, filtered, and evaporated. The crude product was purified by silica gel columnchromatography and recrystallized from appropriate solvent to give the desired compound.

Reference： [1]Amrane, Dyhia; Azas, Nadine; Gellis, Armand; Hutter, Sébastien; Prieri, Marion; Primas, Nicolas; Vanelle, Patrice; Verhaeghe, Pierre [Molecules, 2020, vol. 25, # 17]

79
[ 824-75-9 ]
[ 98-80-6 ]
[ 366-63-2 ]

Yield	Reaction Conditions	Operation in experiment
85%	With dmap; potassium hydroxide In dimethyl sulfoxide at 100℃; for 2h;	General procedure: In a 25-mL round bottom flask, benzamide (0.5 mmol), phenylboronic acid (1 mmol), KOH (1 mmol), a nanocatalyst (30 mol% relative to benzamide substrate), DMAP (20 mol%) and DMSO (2 ml) were added at 100 for a specified time, as monitored by thin-layer-chromatography (TLC). After the completion of the reaction, used external magnet to separate the catalyst. The mixture was diluted with water, and the product was extracted with EtOAc (3×). The combined extracts were washed with brine (3×) and dried over Na2SO4. The product was purified by column chromatography (300 mesh silica gel), eluting with EtOAc-petroleum ether solvent. Unless otherwise noted, materials obtained from commercial suppliers were used without further purification.

Reference： [1]Wang, Xingyang; Liu, Jianhui; An, Guanghui [Tetrahedron Letters, 2020, vol. 61, # 43]

80
[ 824-75-9 ]
[ 1679-18-1 ]
[ 1978-88-7 ]

Yield	Reaction Conditions	Operation in experiment
90%	With dmap; potassium hydroxide In dimethyl sulfoxide at 100℃; for 2h;	General procedure: In a 25-mL round bottom flask, benzamide (0.5 mmol), phenylboronic acid (1 mmol), KOH (1 mmol), a nanocatalyst (30 mol% relative to benzamide substrate), DMAP (20 mol%) and DMSO (2 ml) were added at 100 for a specified time, as monitored by thin-layer-chromatography (TLC). After the completion of the reaction, used external magnet to separate the catalyst. The mixture was diluted with water, and the product was extracted with EtOAc (3×). The combined extracts were washed with brine (3×) and dried over Na2SO4. The product was purified by column chromatography (300 mesh silica gel), eluting with EtOAc-petroleum ether solvent. Unless otherwise noted, materials obtained from commercial suppliers were used without further purification.

Reference： [1]Wang, Xingyang; Liu, Jianhui; An, Guanghui [Tetrahedron Letters, 2020, vol. 61, # 43]

81
[ 824-75-9 ]
[ 63503-60-6 ]
4-fluoro-N-(3-chlorophenyl)benzamide [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
85%	With dmap; potassium hydroxide In dimethyl sulfoxide at 100℃; for 2h;	General procedure: In a 25-mL round bottom flask, benzamide (0.5 mmol), phenylboronic acid (1 mmol), KOH (1 mmol), a nanocatalyst (30 mol% relative to benzamide substrate), DMAP (20 mol%) and DMSO (2 ml) were added at 100 for a specified time, as monitored by thin-layer-chromatography (TLC). After the completion of the reaction, used external magnet to separate the catalyst. The mixture was diluted with water, and the product was extracted with EtOAc (3×). The combined extracts were washed with brine (3×) and dried over Na2SO4. The product was purified by column chromatography (300 mesh silica gel), eluting with EtOAc-petroleum ether solvent. Unless otherwise noted, materials obtained from commercial suppliers were used without further purification.

Reference： [1]Wang, Xingyang; Liu, Jianhui; An, Guanghui [Tetrahedron Letters, 2020, vol. 61, # 43]

82
[ 824-75-9 ]
[ 589-87-7 ]
[ 671-15-8 ]

Yield	Reaction Conditions	Operation in experiment
94%	With caesium carbonate at 120℃; for 14h; Schlenk technique; Inert atmosphere;	4.3. General procedure for the Cu/C catalyzed amidation of aryl iodides with primary amides and lactams General procedure: The aryl iodide (1.5 mmol), amide (1 mmol), Cesium carbonate(1.5 mmol, 489 mg), and Cu/C (50 mg) were weighted into a Schlenk flask (10 mL) with a small magnetic stir bar. The reaction flask was evacuated and backfilled with nitrogen three times, and butyrylonitrile (3 ml) was added by syringe under nitrogen atmosphere. The resulting mixture was sealed under nitrogen and heated at 120 °C for 14 h. The reaction mixture was cooled to room temperature, filtered, and the solvent removed by reduced pressure distillation. The residue was purified by silica gel flash chromatography to get the product.

Reference： [1]Zhao, Rong; Dong, Wenwen; Teng, Jiangge; Wang, Zhiwei; Wang, Yunzhong; Yang, Jianguo; Jia, Qiang; Chu, Changhu [Tetrahedron, 2021, vol. 79]

83
[ 824-75-9 ]
(4-fluorophenyl)methylamine hydrochloride [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
72%	Stage #1: p-fluorobenzamide With bis(cyclopentadienyl)dihydrozirconium; 4,4,5,5-tetramethyl-[1,3,2]-dioxaboralane at 20℃; for 24h; Inert atmosphere; Stage #2: With hydrogenchloride In diethyl ether Inert atmosphere;	68 The bis(cyclopentadiene) zirconium dihydride (denoted as Cp2ZrH2, 0.01mmol, 2.23mg), 4-fluorobenzamide (denoted as 5d, 0.2mmol, 27.8mg) and pinacol borane (denoted as HBpin , 0.6mmol, 87μL), stirred at room temperature under nitrogen (1atm) atmosphere for 24h, treated with hydrogen chloride in ether solution to obtain the hydrochloride compound of formula 6d (white solid, (4-fluorophenyl) methylamine hydrochloride) ). The isolated yield is 72%.

Reference： [1]Current Patent Assignee: CHINESE ACADEMY OF SCIENCES; SUZHOU RES INSTITUTE OF LANZHOU INSTITUTE OF CHEMI - CN112299938, 2021, A Location in patent: Paragraph 0214-0216

84
[ 824-75-9 ]
tert-butyl 4-((6-bromopyridin-2-yl)fluoromethylene)piperidine-1-carboxylate [ No CAS ]
tert-butyl 4-(fluoro(6-(4-fluorobenzamido)pyridin-2-yl)methylene)piperidine-1-carboxylate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
79%	With copper(l) iodide; (R,R)-N,N'-dimethyl-1,2-diaminocyclohexane; potassium carbonate In toluene at 90℃; for 10h; Inert atmosphere;	4.1.4 General procedure for preparation of intermediates 5a-5g General procedure: To a suspension of intermediate 4 (1.00 equiv), corresponding benzamide derivatives (2.00 equiv), K2CO3 (7.00 equiv) and water (50.00 equiv) in toluene (10mL) was added (1R,2R)-N,N′-dimethyl-1,2-cyclohexanediamine (1.00 equiv) and CuI (1.00 equiv) under N2 atmosphere. The reaction mixture was heated to 90°C for 10h, then cooled to rt, filtered, and evaporated. Water (10mL) was added and the mixture was extracted with DCM (10mL×2), the combined organic phases were dried over Na2SO4, filtered, and evaporated. The residue was purified by column chromatography on silica gel using (PE/EA=5:1 (v:v)) as solvent to give intermediates 5a-5g.

Reference： [1]Jin, Chuanfei; Yi, Chao; Zhong, Wenhe; Xue, Yaping; Chen, Kangzhi; Deng, Kang; Wang, Zusheng; Wang, Tao [European Journal of Medicinal Chemistry, 2021, vol. 225]

85
[ 499-90-1 ]
[ 824-75-9 ]

Reference： [1]Organic and Biomolecular Chemistry,2021,vol. 19,p. 10073 - 10080

86
[ 459-56-3 ]
[ 824-75-9 ]
4-fluorobenzyl 4-fluorobenzoate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
92%	With [2-(di-tert-butylphosphinomethyl)-6-(diethylaminomethyl)pyridine]ruthenium(II) chlorocarbonyl hydride; potassium-t-butoxide; ammonia In tert-Amyl alcohol; toluene at 120 - 150℃; for 36h; Green chemistry;

Reference： [1]Ben-David, Yehoshoa; Luo, Jie; Milstein, David; Montag, Michael; Zhou, Quan-Quan [Chemical Science, 2022, vol. 13, # 13, p. 3894 - 3901]

87
[ 57772-50-6 ]
[ 824-75-9 ]
2-(4-fluorophenyl)-8-methylquinazoline [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
93%	With chlorine[2-(4,5-dihydro-1H-imidazol-2-yl)-6-methoxypyridine](pentamethylcyclopentadienyl)iridium(III) chloride; potassium-t-butoxide In 1,4-dioxane at 80℃; for 11h; Schlenk technique;	Quinazolines 3 from 1 and 2; General Procedure General procedure: In a 10.0 mL Schlenk tube, a mixture of 1 (1.0 mmol), 2 (1.1 mmol), t-BuOK (1.1 mmol), 1,4-dioxane (2.0 mL), and TC-6 (0.1 mol%) was reactedat 80 °C in the air. After completion of the reaction, the mixturewas extracted with EtOAc (3 × 10 mL). The combined EtOAc layerswere then dried (MgSO4) and concentrated in vacuum. The resultingcrude product was purified by silica gel chromatography using a mixtureof EtOAc/PE (1:20-1:50).

Reference： [1]Shui, Hongling; Zhong, Yuhong; Ouyang, Lu; Luo, Nianhua; Luo, Renshi [Synthesis, 2022, vol. 54, # 12, p. 2876 - 2884]

88
[ 824-75-9 ]
[ 67-68-5 ]
N,N’-methylenebis(4-fluorobenzamide) [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
93%	With oxalyl dichloride In toluene at 0℃; for 2.5h; Reflux;	4.2. General experimental procedures General procedure: General Procedure for syntheses of methylenebisamides from aimdes and DMSO in Toluene with a substoichiometric amount of (COCl) 2 . To a solution of DMSO (10 mmol, 2 equivalents) in toluene (5 mL) was added dropwise a solution of oxalyl chloride (1.65 mmol, 0.33 equivalents) in toluene (5 mL) at 0 °C. Then a solution of amide (1) (5 mmol, 1 equivalent) in toluene (10 mL) was added subsequently. After addition, the reaction mixture was heated to reflux in an oil bath and monitored by TLC or GC-MS. For the reactions of substrates 1a-cc and all the reactions with DMSO-d6 , the reaction mixture was poured into 120 mL petroleum ether after completion. The precipitated product (2a-2cc and all the deuterated products) was filtered and dried at 45 C in a vac- uum oven for 1 h. The products (2dd and 2ee) were obtained by removing toluene under reduced pressure without further purifi- caiton. The pure products (2ffand 2 gg) were obtained by purifi- cation on flash column chromatography.

Reference： [1]Li, Ning; Liang, Sen; Liu, Yongguo; Peng, Shuai; Sun, Baoguo; Tian, Hongyu; Wang, Hao; Wang, Yutong [Journal of Molecular Structure, 2022, vol. 1263]

Purity	Size	Price	VIP Price	USA Stock *0-1 Day	Global Stock *5-7 Days	Quantity
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CAS No. :	824-75-9	MDL No. :	MFCD00007992
Formula :	C₇H₆FNO	Boiling Point :	-
Linear Structure Formula :	-	InChI Key :	VNDHYTGVCGVETQ-UHFFFAOYSA-N
M.W :	139.13	Pubchem ID :	71572
Synonyms :

Num. heavy atoms :	10
Num. arom. heavy atoms :	6
Fraction Csp3 :	0.0
Num. rotatable bonds :	1
Num. H-bond acceptors :	2.0
Num. H-bond donors :	1.0
Molar Refractivity :	34.49
TPSA :	43.09 Å²

GI absorption :	High
BBB permeant :	Yes
P-gp substrate :	No
CYP1A2 inhibitor :	No
CYP2C19 inhibitor :	No
CYP2C9 inhibitor :	No
CYP2D6 inhibitor :	No
CYP3A4 inhibitor :	No
Log Kp (skin permeation) :	-6.5 cm/s

Log Po/w (iLOGP) :	1.18
Log Po/w (XLOGP3) :	0.91
Log Po/w (WLOGP) :	1.34
Log Po/w (MLOGP) :	1.63
Log Po/w (SILICOS-IT) :	1.4
Consensus Log Po/w :	1.29

[ CAS No. 824-75-9 ] {[proInfo.proName]}

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[ 824-75-9 ] Synthesis Path-Upstream 1~1

[ 824-75-9 ] Synthesis Path-Downstream 1~88

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[ 824-75-9 ]

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Lipinski :	0.0
Ghose :	None
Veber :	0.0
Egan :	0.0
Muegge :	1.0
Bioavailability Score :	0.55

Log S (ESOL) :	-1.65
Solubility :	3.09 mg/ml ; 0.0222 mol/l
Class :	Very soluble
Log S (Ali) :	-1.4
Solubility :	5.53 mg/ml ; 0.0398 mol/l
Class :	Very soluble
Log S (SILICOS-IT) :	-2.24
Solubility :	0.804 mg/ml ; 0.00578 mol/l
Class :	Soluble

PAINS :	0.0 alert
Brenk :	0.0 alert
Leadlikeness :	1.0
Synthetic accessibility :	1.0

Signal Word:	Warning	Class:	N/A
Precautionary Statements:	P261-P305+P351+P338	UN#:	N/A
Hazard Statements:	H315-H319-H335	Packing Group:	N/A
GHS Pictogram:

Precautionary Statements-General
Code	Phrase
P101	If medical advice is needed,have product container or label at hand.
P102	Keep out of reach of children.
P103	Read label before use
Prevention
Code	Phrase
P201	Obtain special instructions before use.
P202	Do not handle until all safety precautions have been read and understood.
P210	Keep away from heat/sparks/open flames/hot surfaces. - No smoking.
P211	Do not spray on an open flame or other ignition source.
P220	Keep/Store away from clothing/combustible materials.
P221	Take any precaution to avoid mixing with combustibles
P222	Do not allow contact with air.
P223	Keep away from any possible contact with water, because of violent reaction and possible flash fire.
P230	Keep wetted
P231	Handle under inert gas.
P232	Protect from moisture.
P233	Keep container tightly closed.
P234	Keep only in original container.
P235	Keep cool
P240	Ground/bond container and receiving equipment.
P241	Use explosion-proof electrical/ventilating/lighting/equipment.
P242	Use only non-sparking tools.
P243	Take precautionary measures against static discharge.
P244	Keep reduction valves free from grease and oil.
P250	Do not subject to grinding/shock/friction.
P251	Pressurized container: Do not pierce or burn, even after use.
P260	Do not breathe dust/fume/gas/mist/vapours/spray.
P261	Avoid breathing dust/fume/gas/mist/vapours/spray.
P262	Do not get in eyes, on skin, or on clothing.
P263	Avoid contact during pregnancy/while nursing.
P264	Wash hands thoroughly after handling.
P265	Wash skin thouroughly after handling.
P270	Do not eat, drink or smoke when using this product.
P271	Use only outdoors or in a well-ventilated area.
P272	Contaminated work clothing should not be allowed out of the workplace.
P273	Avoid release to the environment.
P280	Wear protective gloves/protective clothing/eye protection/face protection.
P281	Use personal protective equipment as required.
P282	Wear cold insulating gloves/face shield/eye protection.
P283	Wear fire/flame resistant/retardant clothing.
P284	Wear respiratory protection.
P285	In case of inadequate ventilation wear respiratory protection.
P231 + P232	Handle under inert gas. Protect from moisture.
P235 + P410	Keep cool. Protect from sunlight.
Response
Code	Phrase
P301	IF SWALLOWED:
P304	IF INHALED:
P305	IF IN EYES:
P306	IF ON CLOTHING:
P307	IF exposed:
P308	IF exposed or concerned:
P309	IF exposed or if you feel unwell:
P310	Immediately call a POISON CENTER or doctor/physician.
P311	Call a POISON CENTER or doctor/physician.
P312	Call a POISON CENTER or doctor/physician if you feel unwell.
P313	Get medical advice/attention.
P314	Get medical advice/attention if you feel unwell.
P315	Get immediate medical advice/attention.
P320
P302 + P352	IF ON SKIN: wash with plenty of soap and water.
P321
P322
P330	Rinse mouth.
P331	Do NOT induce vomiting.
P332	IF SKIN irritation occurs:
P333	If skin irritation or rash occurs:
P334	Immerse in cool water/wrap n wet bandages.
P335	Brush off loose particles from skin.
P336	Thaw frosted parts with lukewarm water. Do not rub affected area.
P337	If eye irritation persists:
P338	Remove contact lenses, if present and easy to do. Continue rinsing.
P340	Remove victim to fresh air and keep at rest in a position comfortable for breathing.
P341	If breathing is difficult, remove victim to fresh air and keep at rest in a position comfortable for breathing.
P342	If experiencing respiratory symptoms:
P350	Gently wash with plenty of soap and water.
P351	Rinse cautiously with water for several minutes.
P352	Wash with plenty of soap and water.
P353	Rinse skin with water/shower.
P360	Rinse immediately contaminated clothing and skin with plenty of water before removing clothes.
P361	Remove/Take off immediately all contaminated clothing.
P362	Take off contaminated clothing and wash before reuse.
P363	Wash contaminated clothing before reuse.
P370	In case of fire:
P371	In case of major fire and large quantities:
P372	Explosion risk in case of fire.
P373	DO NOT fight fire when fire reaches explosives.
P374	Fight fire with normal precautions from a reasonable distance.
P376	Stop leak if safe to do so. Oxidising gases (section 2.4) 1
P377	Leaking gas fire: Do not extinguish, unless leak can be stopped safely.
P378
P380	Evacuate area.
P381	Eliminate all ignition sources if safe to do so.
P390	Absorb spillage to prevent material damage.
P391	Collect spillage. Hazardous to the aquatic environment
P301 + P310	IF SWALLOWED: Immediately call a POISON CENTER or doctor/physician.
P301 + P312	IF SWALLOWED: call a POISON CENTER or doctor/physician IF you feel unwell.
P301 + P330 + P331	IF SWALLOWED: Rinse mouth. Do NOT induce vomiting.
P302 + P334	IF ON SKIN: Immerse in cool water/wrap in wet bandages.
P302 + P350	IF ON SKIN: Gently wash with plenty of soap and water.
P303 + P361 + P353	IF ON SKIN (or hair): Remove/Take off Immediately all contaminated clothing. Rinse SKIN with water/shower.
P304 + P312	IF INHALED: Call a POISON CENTER or doctor/physician if you feel unwell.
P304 + P340	IF INHALED: Remove victim to fresh air and Keep at rest in a position comfortable for breathing.
P304 + P341	IF INHALED: If breathing is difficult, remove victim to fresh air and keep at rest in a position comfortable for breathing.
P305 + P351 + P338	IF IN EYES: Rinse cautiously with water for several minutes. Remove contact lenses, if present and easy to do. Continue rinsing.
P306 + P360	IF ON CLOTHING: Rinse Immediately contaminated CLOTHING and SKIN with plenty of water before removing clothes.
P307 + P311	IF exposed: call a POISON CENTER or doctor/physician.
P308 + P313	IF exposed or concerned: Get medical advice/attention.
P309 + P311	IF exposed or if you feel unwell: call a POISON CENTER or doctor/physician.
P332 + P313	IF SKIN irritation occurs: Get medical advice/attention.
P333 + P313	IF SKIN irritation or rash occurs: Get medical advice/attention.
P335 + P334	Brush off loose particles from skin. Immerse in cool water/wrap in wet bandages.
P337 + P313	IF eye irritation persists: Get medical advice/attention.
P342 + P311	IF experiencing respiratory symptoms: call a POISON CENTER or doctor/physician.
P370 + P376	In case of fire: Stop leak if safe to Do so.
P370 + P378	In case of fire:
P370 + P380	In case of fire: Evacuate area.
P370 + P380 + P375	In case of fire: Evacuate area. Fight fire remotely due to the risk of explosion.
P371 + P380 + P375	In case of major fire and large quantities: Evacuate area. Fight fire remotely due to the risk of explosion.
Storage
Code	Phrase
P401
P402	Store in a dry place.
P403	Store in a well-ventilated place.
P404	Store in a closed container.
P405	Store locked up.
P406	Store in corrosive resistant/ container with a resistant inner liner.
P407	Maintain air gap between stacks/pallets.
P410	Protect from sunlight.
P411
P412	Do not expose to temperatures exceeding 50 oC/ 122 oF.
P413
P420	Store away from other materials.
P422
P402 + P404	Store in a dry place. Store in a closed container.
P403 + P233	Store in a well-ventilated place. Keep container tightly closed.
P403 + P235	Store in a well-ventilated place. Keep cool.
P410 + P403	Protect from sunlight. Store in a well-ventilated place.
P410 + P412	Protect from sunlight. Do not expose to temperatures exceeding 50 oC/122oF.
P411 + P235	Keep cool.
Disposal
Code	Phrase
P501	Dispose of contents/container to ...
P502	Refer to manufacturer/supplier for information on recovery/recycling

[ CAS No. 824-75-9 ] {[proInfo.proName]}

Quality Control of [ 824-75-9 ]

Related Doc. of [ 824-75-9 ]

Product Details of [ 824-75-9 ]

Calculated chemistry of [ 824-75-9 ]

Physicochemical Properties

Pharmacokinetics

Lipophilicity

Druglikeness

Water Solubility

Medicinal Chemistry

Safety of [ 824-75-9 ]

Application In Synthesis of [ 824-75-9 ]

[ 824-75-9 ] Synthesis Path-Upstream 1~1

[ 824-75-9 ] Synthesis Path-Downstream 1~88

Related Functional Groups of [ 824-75-9 ]

Fluorinated Building Blocks

Aryls

Amides

Amines

Precautionary Statements-General

Prevention

Response

Storage

Disposal

Physical hazards

Health hazards

Environmental hazards

Inquiry

Related Functional Groups of
[ 824-75-9 ]