Name: 14763-20-3|(3-Chlorophenyl)hydrazine|98%
Brand: Ambeed
SKU: A515563
Rating: 90 (32 reviews)

1
[ 75055-73-1 ]
[ 14763-20-3 ]
[ 107915-27-5 ]
[ 107915-26-4 ]

Yield	Reaction Conditions	Operation in experiment
	With hydrogenchloride

Reference： [1]Wright et al. [Journal of the American Chemical Society, 1959, vol. 81, p. 5637,5639,5640]

2
[ 141-97-9 ]
[ 14763-20-3 ]
[ 20629-91-8 ]

Yield	Reaction Conditions	Operation in experiment
92%	In neat (no solvent); at 140℃; for 0.00833333h;Irradiation; Green chemistry;	General procedure: A mixture of phenyl hydrazine (1 mmol), ethyl acetoacetate (1 mmol), and cobalt doped ZnS NPs (5 mol%) which was taken in a Borosil beaker. The reaction mixture was homogenized with the help of a glass rod and irradiated in an infrared reactor (360 W). The progress of the reaction was checked on TLC. After completion, the reaction mixture was cooled at room temperature. The resultant material was diluted with water and extracted with ethyl acetate. The organic layer was dried over anhydrous MgSO4, and the solvent was evaporated under reduced pressure to yield the crude product, which was then purified by recrystallization from hot ethanol. Nanoparticles were recovered by sonication of aqueous layer and reutilized four times for the same reaction.

Reference： [1]Journal of Molecular Catalysis A: Chemical,2013,vol. 373,p. 61 - 71
[2]Bioorganic and Medicinal Chemistry,2004,vol. 12,p. 2317 - 2333
[3]Kogyo Kagaku zasshi / Journal of the Society of Chemical Industry,1954,vol. 57,p. 56
Chemisches Zentralblatt,1955,vol. 126,p. 11629
[4]European Journal of Organic Chemistry,2013,p. 5276 - 5281

3
[ 108-42-9 ]
[ 14763-20-3 ]

Yield	Reaction Conditions	Operation in experiment
72%		3-chloroaniline (K-IV) (1 eq., 50 g) was dissolved at -5 to 0 0C in concentrated HCI (300 ml) and stirred for 10 min. A mixture of NaNO2 (1.2 eq., 32.4 g), water (30 ml), SnCI2»2H2O (2.2 eq., 70.6 g) and concentrated HCI (100 ml) was added dropwise over a period of 3 h while maintaining the temperature. After stirring for a further 2 h at -5 to 0 0C, the reaction mixture was set to pH 9 using NaOH solution and extracted with EE (250 ml). The combined organic phases were dried over magnesium sulphate and the solvent was removed under vacuum. The purification by column chromatography (SiO2, 8 % EE/hexane) produced 40 g (72 % yield) of (3-chlorophenyl)hydrazine (K-IV) as a brown oil.
72%		3-chloroaniline (K-IV) (1 equiv., 50 g) was dissolved at -5 to 0 C. in concentrated HCl (300 mL) and stirred for 10 min. A mixture of NaNO2 (1.2 equiv., 32.4 g), water (30 mL), SnCl2.2H2O (2.2 equiv., 70.6 g) and concentrated HCl (100 mL) was added dropwise over a period of 3 h while maintaining the temperature constant. After stirring for a further 2 h at -5 to 0 C., the reaction mixture was adjusted with NaOH solution to pH 9 and extracted with EE (250 mL). The combined organic phases were dried over magnesium sulphate and the solvent was removed in vacuo. The column chromatography purification (SiO2, 8% EE/hexane) yielded 40 g (72% yield) of (3-chlorophenyl)hydrazine (K-IV) as a brown oil.
72%		Step k05: 3-chloroaniline (K-IV) (1 eq., 50 g) was dissolved at -5 to 0 C. in concentrated HCl (300 ml) and stirred for 10 min. A mixture of NaNO2 (1.2 eq., 32.4 g), water (30 ml), SnCl2.2H2O (2.2 eq., 70.6 g) and concentrated HCl (100 ml) was added dropwise over a period of 3 h while maintaining the temperature. After stirring for a further 2 h at -5 to 0 C., the reaction mixture was set to pH 9 using NaOH solution and extracted with EE (250 ml). The combined organic phases were dried over magnesium sulphate and the solvent was removed under vacuum. The purification by column chromatography (SiO2, 8% EE/hexane) produced 40 g (72% yield) of (3-chlorophenyl)hydrazine (K-IV) as a brown oil.

72%		Step k05: 3-chloroaniline (K-IV) (1 eq., 50 g) was dissolved at -5 to 0 C in concentrated HCI (300 ml) and stirred for 10 min. A mixture of NaN02 (1.2 eq., 32.4 g), water (30 ml), SnCI2*2H20 (2.2 eq., 70.6 g) and concentrated HCI (100 ml) was added dropwise over a period of 3 h while maintaining the temperature. After stirring for a further 2 h at -5 to 0 C, the reaction mixture was set to pH 9 using NaOH solution and extracted with EE (250 ml). The combined organic phases were dried over magnesium sulphate and the solvent was removed under vacuum. The purification by column chromatography (Si02, 8 % EE/hexane) produced 40 g (72 % yield) of (3-chlorophenyl)hydrazine (K-IV) as a brown oil.
72%		3-chloroaniline (K-IV) (1 eq., 50 g) was dissolved at -5 to 0 C in concentrated HCI (300 ml) and stirred for 10 min. A mixture of NaN02 (1.2 eq., 32.4 g), water (30 ml), SnCI2'2H20 (2.2 eq., 70.6 g) and concentrated HCI (100 ml) was added dropwise over a period of 3 h while maintaining the temperature. After stirring for a further 2 h at -5 to 0 C, the reaction mixture was set to pH 9 using NaOH solution and extracted with EE (250 ml). The combined organic phases were dried over magnesium sulphate and the solvent was removed under vacuum. The purification by column chromatography (Si02, 8 % EE/hexane) produced 40 g (72 % yield) of (3-chlorophenyl)hydrazine (K-IV) as a brown oil.
72%		Step k05: 3-chloroaniline (K-IV) (1 eq., 50 g) was dissolved at -5 to 0 C. in concentrated HCl (300 ml) and stirred for 10 min. A mixture of NaNO2 (1.2 eq., 32.4 g), water (30 ml), SnCl2.2H2O (2.2 eq., 70.6 g) and concentrated HCl (100 ml) was added dropwise over a period of 3 h while maintaining the temperature. After stirring for a further 2 h at -5 to 0 C., the reaction mixture was set to pH 9 using NaOH solution and extracted with EE (250 ml). The combined organic phases were dried over magnesium sulfate and the solvent was removed under vacuum. The purification by column chromatography (SiO2, 8% EE/hexane) produced 40 g (72% yield) of (3-chlorophenyl)hydrazine (K-IV) as a brown oil.
72%		3-chloroaniline (K-IV) (1 equivalent, 50 g) was dissolved at -5 to 0 C in concentrated HCI (300 mL) and stirred for 10 min. A mixture of NaN02 (1.2 equivalents, 32.4 g), water (30 mL), SnCI2*2H20 (2.2 equivalents, 70.6 g) and concentrated HCI (100 mL) was added dropwise over a period of 3 h while maintaining the temperature. After stirring for a further 2 h at -5 to 0 C, the reaction mixture was set to pH 9 using NaOH solution and extracted with ethyl acetate (250 mL). The combined organic phases were dried over magnesium sulphate and the solvent was removed under vacuum. The purification by column chromatography (silica gel: 100-200 mesh, eluent: 8 % ethyl acetate/n-hexane) produced 40 g (72 %) of (3-chlorophenyl)hydrazine (K-IV) as a brown oil. Step k02: The aldehyde (K-l) (2 equivalents, 300 mL) obtained from k01 and (3- chlorophenyl)hydrazine (K-IV) (1 equivalent, 20 g) were placed in ethanol (200 mL) and refluxed for 5 h. The solvent was removed under vacuum, the residue was purified by column chromatography (silica gel: 100-200 mesh, eluent: n-hexane) and the product (25 g, 72 %) K-ll was obtained as a brown oil.
72%		Step k05 3-chloroaniline (K-IV) (1 equivalent, 50 g) was dissolved at -5 to 0 C. in concentrated HCl (300 mL) and stirred for 10 min. A mixture of NaNO2 (1.2 equivalents, 32.4 g), water (30 mL), SnCl2.2H2O (2.2 equivalents, 70.6 g) and concentrated HCl (100 mL) was added dropwise over a period of 3 h while maintaining the temperature. After stirring for a further 2 h at -5 to 0 C., the reaction mixture was set to pH 9 using NaOH solution and extracted with ethyl acetate (250 mL). The combined organic phases were dried over magnesium sulfate and the solvent was removed under vacuum. The purification by column chromatography (silica gel: 100-200 mesh, eluent: 8% ethyl acetate/n-hexane) produced 40 g (72%) of (3-chlorophenyl)hydrazine (K-IV) as a brown oil.
72%	With hydrogenchloride; tin(II) chloride dihdyrate; sodium nitrite; In water; at -5 - 0℃; for 5h;	3-chloroaniline (K-IV) (1 equivalent, 50 g) was dissolved at -5 to 0 C in concentrated HCI (300 mL) and stirred for 10 min. A mixture of NaN02 (1 .2 equivalents, 32.4 g), water (30 mL), SnCI2-2H20 (2.2 equivalents, 70.6 g) and concentrated HCI (100 mL) was added dropwise over a period of 3 h while maintaining the temperature. After stirring for a further 2 h at -5 to 0 C, the reaction mixture was set to pH 9 using NaOH solution and extracted with ethyl acetate (250 mL). The combined organic phases were dried over magnesium sulphate and the solvent was removed under vacuum. The purification by column chromatography (silica gel: 100-200 mesh, eluent: 8 % ethyl acetate/n-hexane) produced 40 g (72 %) of (3-chlorophenyl)hydrazine (K-IV) as a brown oil.
72%		Step k05: 3-chloroaniline (K-IV) (1 equivalent, 50 g) was dissolved at -5 to 0 C in concentrated HCI (300 mL) and stirred for 10 min. A mixture of NaN02 (1 .2 equivalents, 32.4 g), water (30 mL), SnCI2-2H20 (2.2 equivalents, 70.6 g) and concentrated HCI (100 mL) was added dropwise over a period of 3 h while maintaining the temperature. After stirring for a further 2 h at -5 to 0 C, the reaction mixture was set to pH 9 using NaOH solution and extracted with ethyl acetate (250 mL). The combined organic phases were dried over magnesium sulphate and the solvent was removed under vacuum. The purification by column chromatography (silica gel: 100-200 mesh, eluent: 8 % ethyl acetate/n-hexane) produced 40 g (72 %) of (3-chlorophenyl)hydrazine (K-IV) as a brown oil.
72%		Step k05: 3-chloroaniline (K-IV) (1 equivalent, 50 g) was dissolved at -5 to 0 C in concentrated HCl (300 mL) and stirred for 10 min. A mixture of NaNO2 (1 .2 equivalents, 32.4 g), water (30 mL), SnCl2-2H2O (2.2 equivalents, 70.6 g) and concentrated HCl (100 mL) was added dropwise over a period of 3 h while maintaining the temperature. After stirring for a further 2 h at -5 to 0C , the reaction mixture was set to pH 9 using NaOH solution and extracted with ethyl acetate (250 mL). The combined organic phases were dried over magnesium sulphate and the solvent was removed under vacuum. The purification by column chromatography (silica gel: 100-200 mesh, eluent: 8 % ethyl acetate/n-hexane) produced 40 g (72 %) of (3-chlorophenyl)hydrazine (K-IV) as a brown oil.
72%		3-chloroaniline (K-IV) (1 equivalent, 50 g) was dissolved at -5 to 0 C in concentrated HCI (300 mL) and stirred for 10 min. A mixture of NaN02 (1 .2 equivalents, 32.4 g), water (30 mL), SnCI2-2H20 (2.2 equivalents, 70.6 g) and concentrated HCI (100 mL) was added dropwise over a period of 3 h while maintaining the temperature. After stirring for a further 2 h at -5 to 0 '?, the reaction mixture was set to pH 9 using NaOH solution and extracted with ethyl acetate (250 mL). The combined organic phases were dried over magnesium sulphate and the solvent was removed under vacuum. The purification by column chromatography (silica gel: 100-200 mesh, eluent: 8 % ethyl acetate/n-hexane) produced 40 g (72 %) of (3-chlorophenyl)hydrazine (K-IV) as a brown oil
72%		Step k05: 3-chloroaniline (K-IV) (1 equivalent, 50 g) was dissolved at -5 to 0 C in concentrated HCL (300 mL) and stirred for 10 min. A mixture of NaNO2 (1 .2 equivalents, 32.4 g), water (30 mL), SnCI2-2H2O (2.2 equivalents, 70.6 g) and concentrated HCl (100 mL) was added dropwise over a period of 3 h while maintaining the temperature. After stirring for a further 2 h at -5 to 0 C, the reaction mixture was set to pH 9 using NaOH solution and extracted with ethyl acetate (250 mL). The combined organic phases were dried over magnesium sulphate and the solvent was removed under vacuum. The purification by column chromatography (silica gel: 100-200 mesh, eluent: 8 % ethyl acetate/n-hexane) produced 40 g (72 %) of (3-chlorophenyl)hydrazine (K-IV) as a brown oil.
		General procedure: Substituted aniline 4a-4s (50 mmol) was dissolved in the 50 mL HCl (18%, aqueous) in the icebath. NaNO2 (50 mmol) dissolved in 50 mL water was added dropwise. The reaction mixture wasstirred for 1 h to obtain a clear solution. Then the solution of SnCl2 (0.1 mol) in 30 mL of concentratedHCl was added dropwise at 0 C. The mixture was stirred at room temperature for 2 h. Afterwards,the mixture was extracted with 50 mL EtOAc and the organic impurities were discarded. Then thesolution was basified with NaOH (40%, aqueous) until it reached pH 7.0. The reaction mass wasextracted with EtOAc three times. Finally, substituted phenylhydrzine 5a-5s was afforded after beingvapored under reduced pressure (in 55%-80% yield) [12].
237 g		A process for the preparation of 3-chlorophenylhydrazine phosphate, comprising the steps of: diazotization500 g of 3-chloroaniline and 1500 ml of 37% concentrated hydrochloric acid were added to a 10 L three-necked flask. The mixture was cooled to 2 C with ice-salt and 857 g of a 35% aqueous solution of sodium nitrite was added while stirring, and the reaction was continued at 0-5 C for 1.5 hours. reductionTo the reaction solution was added 730 ml of concentrated hydrochloric acid, 730 ml of water and 480 g of zinc powder, and the reaction was allowed to proceed until the reaction was completed at 18 C. The reaction solution became grayish white, and then 30% sodium hydroxide solution was added until the pH of the reaction solution was 10 , 5 C for 2 hours, the precipitation of crystals, filtered to obtain 294g 3 - chlorophenyl hydrazine crude. purificationThe 294g 3-chlorophenyl hydrazine crude dissolved in 5880g of water, heated to 60 C to completely dissolve, then add the appropriate amount of activated carbon decolorization 20 minutes, hot filtered to colorless filtrate, 5 C for 2 hours, precipitated crystals, filtered to 237g Pure phenylhydrazine. into the saltPure 237g 3-chlorophenyl hydrazine dissolved in 403ml of 40% phosphoric acid, stirring at 65 C until the reaction solution precipitation crystallization, cooling to 20 C, filtration, rinse with acetone filter cake, dry after 3-chlorophenyl hydrazine phosphate Salt finished 380g, content of 99.3%Yield 42.6%.
240 g		diazotization10 g of a three-necked flask was charged with 500 g of 3-chloroaniline and 1500 ml of 37% concentrated hydrochloric acid,Cooled with ice salt to 2 C,Add with stirring35% aqueous solution of sodium nitrite,The temperature was maintained at 0 to 5 C for 1.5 hours. reductionTo the reaction solution was added 730 ml of 37% concentrated hydrochloric acid,730 ml of water and 480 g of zinc powder,Keep the temperature at 18 CReaction to complete reaction,The reaction liquid becomes off-white,And then add 30% sodium hydroxide solution to the reaction solution PH value of 10,5 for 2 hours,Precipitation of crystals,Filtration of 290g 3-chlorophenylhydrazine crude. purificationThe crude product of 290g 3-chlorophenylhydrazine dissolved in 5800g water, heated to 60 C to completely dissolve, then add appropriate amount of activated carbon decolorization for 20 minutes, hot filter to a colorless filtrate, 5 insulation 2 hours, precipitation of crystals,Filtration of 240g 3-chlorophenylhydrazine pure.

Reference： [1]Patent: WO2010/127855,2010,A1 .Location in patent: Page/Page column 98
[2]Patent: US2012/46301,2012,A1 .Location in patent: Page/Page column 29
[3]Patent: US2012/115903,2012,A1 .Location in patent: Page/Page column 34
[4]Patent: WO2012/62463,2012,A1 .Location in patent: Page/Page column 75
[5]Patent: WO2012/62462,2012,A1 .Location in patent: Page/Page column 76
[6]Patent: US2012/115893,2012,A1 .Location in patent: Page/Page column 30
[7]Patent: WO2013/13815,2013,A1 .Location in patent: Page/Page column 106
[8]Patent: US2013/29962,2013,A1 .Location in patent: Paragraph 0679
[9]Patent: WO2013/68463,2013,A1 .Location in patent: Page/Page column 48
[10]Patent: WO2013/68461,2013,A1 .Location in patent: Page/Page column 69; 70
[11]Patent: WO2013/68467,2013,A1 .Location in patent: Page/Page column 50
[12]Patent: WO2013/68464,2013,A1 .Location in patent: Page/Page column 51
[13]Patent: WO2013/68462,2013,A1 .Location in patent: Page/Page column 58; 59
[14]Bioorganic and Medicinal Chemistry,2004,vol. 12,p. 2317 - 2333
[15]Journal fur praktische Chemie (Leipzig 1954),1891,vol. <2>44,p. 458
[16]Chemistry of Heterocyclic Compounds,1986,vol. 22,p. 713 - 722
Khimiya Geterotsiklicheskikh Soedinenii,1986,vol. 22,p. 898 - 907
[17]Journal of Medicinal Chemistry,1991,vol. 34,p. 2892 - 2898
[18]Synthetic Communications,1985,vol. 15,p. 697 - 706
[19]Molecules,2016,vol. 21
[20]Patent: CN105272877,2016,A .Location in patent: Paragraph 0040; 0041; 0042; 0043; 0044; 0045; 0046; 0047
[21]Patent: CN105294486,2016,A .Location in patent: Paragraph 0040-0047

4
[ 119-67-5 ]
[ 14763-20-3 ]
2-(3-chlorophenyl)phthalazin-1(2H)-one [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
91.53%	at 105℃; for 1.25h;	Will be 2.85g (20mmol)M-chlorobenzoquinone3.00g (20mmol) o-carboxybenzaldehyde was added to a 10mL single-mouth round bottomIn the bottle, heat to 105 C, heat-reacting reaction for 75 minutes under mechanical stirring, TLC or gas phase monitoring reaction, after the reaction is over, the reaction3 mL of ethanol was added to the system, stirred for 0.5 hours, allowed to stand, and filtered to obtain 4.69 g of an orange solid.That is, target compound 8,The yield was 91.53%.

Reference： [1]Patent: CN108264488,2018,A .Location in patent: Paragraph 0069; 0070
[2]Journal of the Chemical Society,1948,p. 597,599

5
[ 333-20-0 ]
[ 14763-20-3 ]
[ 828-11-5 ]

Reference： [1]Parikh,P.M.; Deliwala,C.V. [Indian Journal of Chemistry, 1965, vol. 3, p. 45 - 46]

6
[ 5784-45-2 ]
[ 14763-20-3 ]
N-(3-Chloro-phenyl)-N'-phthalazin-1-yl-hydrazine [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
66%	In ethanol for 4h; Heating;

Reference： [1]Tarzia; Occelli; Corsico; Gallico; Luzzani; Barone [Il Farmaco, 1989, vol. 44, # 1, p. 17 - 28]

7
[ 108-94-1 ]
[ 14763-20-3 ]
[ 36684-66-9 ]
[ 68985-43-3 ]

Yield	Reaction Conditions	Operation in experiment
	With 2,4,6-tripropyl-1,3,5,2,4,6-trioxatriphosphinane-2,4,6-trioxide; In ethyl acetate; at 110℃; for 0.166667h;Microwave irradiation; Sealed vessel;	General procedure: T3P (50% in EtOAc) (0.55-0.68 mmol) was added to a mixture of hydrazine (59 mg, 0.55 mmol) and ketone/aldehyde (0.55 mmol) in a microwave vial. The reaction volume was then made up to 0.5 mL with EtOAc and the vessel was sealed under air. The mixture was heated under microwave irradiation (Biotage Initiator) at 100-150 C for 5-15 min. The solvent was evaporated under reduced pressure and the oily residue was purified by filtration through a plug of silica gel (eluent: isohexane/EtOAc, 8:2) to yield the desired indole or tetrahydrocarbazole. When the reaction was conducted on a 5 mmol scale the product (3a) was purified by precipitation from acetone/water.

Reference： [1]Chemistry of Heterocyclic Compounds,1986,vol. 22,p. 713 - 722
Khimiya Geterotsiklicheskikh Soedinenii,1986,vol. 22,p. 898 - 907
[2]Chemistry of Heterocyclic Compounds,1986,vol. 22,p. 713 - 722
Khimiya Geterotsiklicheskikh Soedinenii,1986,vol. 22,p. 898 - 907
[3]Tetrahedron Letters,2011,vol. 52,p. 4417 - 4420

8
[ 614-16-4 ]
[ 14763-20-3 ]
[ 72411-49-5 ]

Yield	Reaction Conditions	Operation in experiment
47%	In ethanol; acetic acid for 3h; Heating;

Reference： [1]Simay, A.; Takacs, K.; Horvath, K.; Dvortsak, P. [Acta Chimica Academiae Scientiarum Hungaricae, 1980, vol. 105, p. 127 - 140]

9
[ 122-51-0 ]
[ 14763-20-3 ]
[ 109-77-3 ]
[ 51516-68-8 ]

Reference： [1]Journal of Medicinal Chemistry,1991,vol. 34,p. 2892 - 2898

10
[ 123-06-8 ]
[ 14763-20-3 ]
[ 51516-68-8 ]

Reference： [1]Journal of Medicinal Chemistry,1991,vol. 34,p. 2892 - 2898
[2]Chemical Biology and Drug Design,2014,vol. 83,p. 272 - 277
[3]RSC Advances,2016,vol. 6,p. 24491 - 24500

11
[ 38768-08-0 ]
[ 14763-20-3 ]
[ 53526-92-4 ]

Reference： [1]Chemistry Letters,1986,p. 1577 - 1580

12
[ 150258-20-1 ]
[ 14763-20-3 ]
2-(3-Chloro-phenyl)-6,8-difluoro-2,5-dihydro-pyrazolo[4,3-c]quinolin-3-one [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
60%	In ethanol

Reference： [1]Savini; Massarelli; Corti; Pellerano; Bruni; Romeo [Il Farmaco, 1993, vol. 48, # 12, p. 1675 - 1686]

13
[ 65112-88-1 ]
[ 14763-20-3 ]
3,5-dihydro-2-(3-chlorophenyl)-1H-pyrazolo<3,4-c>quinoline-1,4-(2H)-dione [ No CAS ]

Reference： [1]Journal of Medicinal Chemistry,1995,vol. 38,p. 2239 - 2243

14
[ 69922-28-7 ]
[ 14763-20-3 ]
C₁₄H₁₂ClN₃O₃ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
83%	In toluene for 3h; Heating;

Reference： [1]Nalawde, Yogesh Madhukar; Joshi, Vidya [Indian Journal of Chemistry - Section B Organic and Medicinal Chemistry, 1998, vol. 37, # 3, p. 310 - 313]

15
[ 2689-69-2 ]
[ 14763-20-3 ]
3-[(3-chloro-phenyl)-hydrazono]-tetrahydro-thiophene-2-carboxylic acid methyl ester [ No CAS ]

Reference： [1]Bioorganic and Medicinal Chemistry Letters,2003,vol. 13,p. 2591 - 2594

16
[ 391-12-8 ]
[ 14763-20-3 ]
3-[(3-chloro-phenyl)-hydrazono]-7-trifluoromethyl-1,3-dihydro-indol-2-one [ No CAS ]

Reference： [1]Angewandte Chemie - International Edition,2003,vol. 42,p. 4479 - 4482

17
[ 14763-20-3 ]
[ 10537-08-3 ]

Reference： [1]Journal of the Chemical Society,1937,p. 1125,1127

18
[ 25784-83-2 ]
[ 14763-20-3 ]
4-chloro-3-[(4-chlorophenyl)thio]-2-methyl-1H-indole [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
		To a suspension of (3-chlorophenyl) -hydrazine hydrochloride (2 g) in acetic acid (30 ml) was added [1- [ (4-CHLOROPHENYL)] thio] -acetone (2.24 g), acetonitrile (20 ml) and water (10 ml). The mixture was strirred at room temperature overnight. The reaction mixture was concentrated in vacuo and the residue suspended in EtOAc, washed with sodium hydrogen carbonate solution, brine, dried [(MGSO4)] and concentrated in vacuo. The residue was dissolved in acetic acid (20 ml) and heated to [80C] overnight. The reaction mixture was poured into water, basified using NaOH and the organics extracted into EtOAc. The EtOAc was washed with brine, dried [(MGS04)] and concentrated in vacuo. Purification by Flash column chromatography (10% EtOAc/hexane as eluent) gave the sub-title compound (0. [816] g). [1H NMR CDC13] : [8] 8. 38 (s, 1H), 7.27-7. 23 (m, 1H), 7.14-7. 07 [(M,] 4H), 6.96 (dt, 2H), 2.52 (s, 3H)

Reference： [1]Patent: WO2003/101961,2003,A1 .Location in patent: Page 22

19
[ 335064-80-7 ]
[ 14763-20-3 ]
C₁₉H₂₂ClN₅ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
20%		To a solution of 100 mg (0.4 mmol) of the step A compound and 72 mg (0.4 mmol) <strong>[14763-20-3]3-chlorophenylhydrazine</strong> in 20 mL of ethanol was added 6 muL of methansulfonic acid (J. P. Bouillon, C. Ates, Z. Janousek, H. G. Viehe, Tetrahedron Lett. 34, 1993, 5075). The solution was stirred for 4 hrs at ambient temperature, 100 muL of pyridine was added and concentrated. The residue was taken up with 10 mL of pyridine and 135 mg (0.88 mmol) of POCl3 at ambient temperature. The resulting red mixture was stirred for 18 hrs at ambient temperature and concentrated. The residue was taken up with 10% methanol in water and purified by preparative HPLC to give 30 mg (20%) of the title compound; MS: m/z 356 (M+H)+.

Reference： [1]Patent: US6887870,2005,B1 .Location in patent: Page/Page column 18; 114

20
[ 67-64-1 ]
[ 14763-20-3 ]
[ 67175-12-6 ]

Yield	Reaction Conditions	Operation in experiment
100%	In water; for 2h;Heating / reflux;	A solution of <strong>[14763-20-3]3-chlorophenylhydrazine</strong> (0.5 g) in 5 mL acetone-water (1:1) was heated at reflux temperature for 2 h and concetrated to afford the corresponding acetone hydrazone as an orange gummy solid (quantitative crude yield). To a portion of this material (0.1 g, 0.55 mmol) in 1 mL toluene was added a solution of acetylisocyanate (102 mg, 1.2 mmol) in 0.25 mL toluene at RT and the mixture was heated at 105 C. for 5 h in a sealed tube. The mixture was concentrated and the gummy residue was extracted with ether. The ether extract was concentrated to afford the title compound as pale gummy solid (80 mg).

Reference： [1]Patent: US6887870,2005,B1 .Location in patent: Page/Page column 151

21
[ 333418-58-9 ]
[ 14763-20-3 ]
[ 863609-02-3 ]

Yield	Reaction Conditions	Operation in experiment
40%	With benzotriazol-1-ol; 1-ethyl-(3-(3-dimethylamino)propyl)-carbodiimide hydrochloride; N-ethyl-N,N-diisopropylamine; In DMF (N,N-dimethyl-formamide); acetonitrile; for 1.5h;	Example 11; N'- (3-Chlorophenyl)-2- [ (4-methyl-5-pyridin-3-yl-4H-1, 2,4-triazol-3- yl) thio] acetohydrazide; Crude [ (4-methyl-5-pyridin-3-yl-4H-1, 2,4-triazol-3-yl) thio] acetic acid from the previous step was dissolved under argon in DMF/MeCN (20 mL/20mL), followed by addition of 1.04 g (7. 81 mmol) HOBt, 1.40 g (7.30 mmol) EDCI, 2 mL (20.6 mmol) DEA and 0.85 g (7.86 mmol) <strong>[14763-20-3]3-chlorophenylhydrazine</strong>. After stirring for 1.5 hours the volume was reduced in vacuo and diluted with water. Extraction with EA, followed by washing with Na2C03, citric acid and finally brine gave after evaporation a crude which was purified over silica (DCM/MeOH=30/1) yielding 1.07 g (40%) of the title compound. 1H-NMR (DMSO-D6): 8. 89-8. 93 (m, 1 H), 8.74 (dd, 1 H), 8. 07-8.18 (m, 2 H), 7.60 (dd, 1 H), 7.09 (t, 1 H), 6.62 - 6. 74 (m, 3 H), 4.03 (s, 2 H), 3.65 (s, 4 H).

Reference： [1]Patent: WO2005/80379,2005,A1 .Location in patent: Page/Page column 42

22
aqueous glyoxylic acid [ No CAS ]
[ 14763-20-3 ]
2-(3-chlorophenyl)hydrazinoacetic acid [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
58.4%	With sodium hydroxide; In ethanol; water;	21-1. Production of 2-(3-chlorophenyl)hydrazinoacetic acid STR182 In 50 ml of ethanol was dissolved 15.0 g (0.11 mole) of <strong>[14763-20-3]3-chlorophenylhydrazine</strong>, followed by adding dropwise thereto 19.5 g (0.11 mole) of a 40% aqueous glyoxylic acid solution and a solution of 4.2 g (0.11 mole) of sodium hydroxide in 20 ml of water under ice-cooling, and the reaction was carried out at room temperature for 2 hours. After completion of the reaction, 80 ml of water was added to the reaction solution and the desired compound was extracted with ethyl acetate (100 ml*2). The organic layer was washed with water, dried over anhydrous magnesium sulfate, and then distilled under reduced pressure to remove the solvent. The crystals thus obtained were washed with an ether-ethyl acetate mixed solution to obtain 12.2 g of the desired compound. Yield 58.4%. 1 H-NMR [CDCl3 /TMS, delta values (ppm)] 2.05 (bs, 1H), 6.98-7.01 (m, 2H), 7.08 (s, 1H), 7.18-7.25 (m, 2H), 8.50 (s, 1H).

Reference： [1]Patent: US5608109,1997,A

23
[ 29124-56-9 ]
[ 14763-20-3 ]
2-Amino-5-bromoacetophenone 3-chlorophenylhydrazone [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	With acetic acid In ethanol; water	5 2-Amino-5-bromoacetophenone 3-chlorophenylhydrazone EXAMPLE 5 2-Amino-5-bromoacetophenone 3-chlorophenylhydrazone A mixture of 3.77 g 2-amino-5-bromoacetophenone and 2.59 g 3-chlorophenylhydrazine in 20 ml EtOH and 4 ml HOAc was refluxed for forty-five minutes. The cooled reaction mixture was diluted with 120 ml of water, and the precipitate was collected, washed with water, and dried to give 5.40 g solid. Recrystallization from methanol gave 1.42 g solid, m.p. 115°-117° C. ANALYSIS: Calculated for C14 H13 BrClN3: 49.66%C; 3.81%H; 12.41%N. Found: 49.61%C; 4.07%H; 12.21%N.

Reference： [1]Current Patent Assignee: SANOFI - US5166170, 1992, A

24
[ 631-31-2 ]
[ 14763-20-3 ]
[ 1034317-08-2 ]

Yield	Reaction Conditions	Operation in experiment
71%	In water at 180℃; for 1h;

Reference： [1]Kaminski, Krzysztof; Obniska, Jolanta [Bioorganic and Medicinal Chemistry, 2008, vol. 16, # 9, p. 4921 - 4931]

25
[ 597-43-3 ]
[ 14763-20-3 ]
[ 1034317-00-4 ]

Yield	Reaction Conditions	Operation in experiment
70%	In water at 180℃; for 1h;

Reference： [1]Kaminski, Krzysztof; Obniska, Jolanta [Bioorganic and Medicinal Chemistry, 2008, vol. 16, # 9, p. 4921 - 4931]

26
[ 138163-08-3 ]
[ 14763-20-3 ]
[ 1093956-68-3 ]
C₂₀H₂₁ClN₂O₂ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
		3-Chlorophenyl)hydrazine (1.3 g, 7.3 mmol, 1 eq.) was mixed with phenylmethyl 4-formyl-1-piperidinecarboxylate (1. 8 g, 7.3 mmol, 1 eq.) in DCM with trifluoroacetic acid (TFA, 8.3 g, 73 mmol, 10 eq.) and refluxed with stirring for 1/2 h. Sodium borohydride (0.831 g, 21.8 mmol, 3 eq.) was then added to the mixture and after 10 min the mixture was transferred to an ice water bath. Excess 28-30% ammonium hydroxide was then added portionwise followed by water. The mixture was shaken and the organic layer separated and dried over sodium sulfate followed by evaporation. The residue was loaded onto silica and purified by normal phase chromatography, eluding with 15, 20, 25% EtOAc/hexanes, eluding first the desired 6-Cl isomer followed by the 4-Cl isomer. The 6-Cl isomer was isolated for further use. MS (ES) m/e 357 [M+H]+.

Reference： [1]Journal of Medicinal Chemistry,2019,vol. 62,p. 3407 - 3427
[2]Patent: US2008/318990,2008,A1 .Location in patent: Page/Page column 18-19

27
[ 14763-20-3 ]
4,4,4-trifluoro-2-methyl-3-oxobutanenitrile [ No CAS ]
[ 1254716-68-1 ]

Yield	Reaction Conditions	Operation in experiment
65%		A step-a product (10 g, 0.066 mol) was taken in ethanolic HCI (300 ml, 30 times) and <strong>[14763-20-3]3-chlorophenyl hydrazine</strong> (9.43 g, 0.066 mol, 1 eq) was added. The reaction mixture was heated to reflux for 2 hrs. Progress of the reaction was monitored by TLC (20% ethyl acetate/hexane, Rr0.3). On completion of the reaction, reaction contents were concentrated and the residue taken in water (200 ml). Basified the contents to a pH~12 with 1 N NaOH solution and filtered the contents. Solid obtained was taken in ethyl acetate (200 ml), dried the contents over sodium sulfate and concentrated under reduced pressure to yield the required product as a red colored solid (12 g, 65% yield).
65%		A step-a product (10 g, 0.066 mol) was taken in ethanolic HCI (300 ml, 30 times) and <strong>[14763-20-3]3-chlorophenyl hydrazine</strong> (9.43 g, 0.066 mol, 1 eq) was added. The reaction mixture was heated to reflux for 2 hrs. Progress of the reaction was monitored by TLC (20% ethyl acetate/hexane, Rp-0.3). On completion of the reaction, reaction contents were concentrated and the residue taken in water (200 ml). Basified the contents to a pH~12 with 1N NaOH solution and filtered the contents. Solid obtained was taken in ethyl acetate (200 ml), dried the contents over sodium sulfate and concentrated under reduced pressure to yield the required product as a red colored solid (12 g, 65% yield).
65%		4,4,4-trifluoro-2-methyl-3-oxobutanenitrile (10 g, 66 mmol, 1 equiv.) was taken up in ethanolic HCl solution (300 mL) and <strong>[14763-20-3]3-chlorophenylhydrazine</strong> (9.43 g, 66 mmol, 1 equiv.) was added. After stirring for 2 h under reflux the solvent was removed in vacuo and the resultant residue was taken up in water (200 mL). After adjusting the pH to 12 by means of 1 N NaOH a solid was obtained by filtration. This was taken up in EtOAc (200 mL) and the solution was dried over sodium sulphate and concentrated by evaporation in vacuo. The product was obtained as a red solid (12 g, 65% yield).

65%		Step b: A step-a product (10 g, 0.066 mol) was taken in ethanolic HCl (300 ml, 30 times) and <strong>[14763-20-3]3-chlorophenyl hydrazine</strong> (9.43 g, 0.066 mol, 1 eq) was added. The reaction mixture was heated to reflux for 2 hrs. Progress of the reaction was monitored by TLC (20% ethyl acetate/hexane, Rf0.3). On completion of the reaction, reaction contents were concentrated and the residue taken in water (200 ml). Basified the contents to a pH12 with 1N NaOH solution and filtered the contents. Solid obtained was taken in ethyl acetate (200 ml), dried the contents over sodium sulfate and concentrated under reduced pressure to yield the required product as a red colored solid (12 g, 65% yield).
65%		Step b: A step-a product (10 g, 0.066 mol) was taken in ethanolic HCI (300 ml, 30 times) and <strong>[14763-20-3]3-chlorophenyl hydrazine</strong> (9.43 g, 0.066 mol, 1 eq) was added. The reaction mixture was heated to reflux for 2 hrs. Progress of the reaction was monitored by TLC (20% ethyl acetate/hexane, Rf~0.3). On completion of the reaction, reaction contents were concentrated and the residue taken in water (200 ml). Basified the contents to a pH~12 with 1 N NaOH solution and filtered the contents. Solid obtained was taken in ethyl acetate (200 ml), dried the contents over sodium sulfate and concentrated under reduced pressure to yield the required product as a red colored solid (12 g, 65% yield).
65%		A step-a product (10 g, 0.066 mol) was taken in ethanolic HCI (300 ml, 30 times) and <strong>[14763-20-3]3-chlorophenyl hydrazine</strong> (9.43 g, 0.066 mol, 1 eq) was added. The reaction mixture was heated to reflux for 2 hrs. Progress of the reaction was monitored by TLC (20% ethyl acetate/hexane, Rr0.3). On completion of the reaction, reaction contents were concentrated and the residue taken in water (200 ml). Basified the contents to a pH~12 with 1N NaOH solution and filtered the contents. Solid obtained was taken in ethyl acetate (200 ml), dried the contents over sodium sulfate and concentrated under reduced pressure to yield the required product as a red colored solid (12 g, 65% yield).
65%		Step b: A step-a product (10 g, 0.066 mol) was taken in ethanolic HCl (300 ml, 30 times) and <strong>[14763-20-3]3-chlorophenyl hydrazine</strong> (9.43 g, 0.066 mol, 1 eq) was added. The reaction mixture was heated to reflux for 2 hrs. Progress of the reaction was monitored by TLC (20% ethyl acetate/hexane, Rf0.3). On completion of the reaction, reaction contents were concentrated and the residue taken in water (200 ml). Basified the contents to a pH12 with 1N NaOH solution and filtered the contents. Solid obtained was taken in ethyl acetate (200 ml), dried the contents over sodium sulfate and concentrated under reduced pressure to yield the required product as a red colored solid (12 g, 65% yield).
65%	With hydrogenchloride; In ethanol; for 2h;Reflux;	A step-a product (10 g, 0.066 mol) was taken in ethanolic HCI (300 mL) and 3- chlorophenyl hydrazine (9.43 g, 0.066 mol, 1 equivalent) was added. The reaction mixture was heated to reflux for 2 h. Progress of the reaction was monitored by TLC (20 % ethyl acetate in n-hexane). On completion of the reaction, reaction contents were concentrated and the residue taken in water (200 mL). Basified the contents to a pH~12 with 1 N NaOH solution and filtered the contents. Solid obtained was taken in ethyl acetate (200 mL), dried the contents over sodium sulphate and concentrated under reduced pressure to yield the required product as a red colored solid (12 g, 65 %).
65%	With hydrogenchloride; In ethanol; for 2h;Reflux;	Step b: A step-a product (10 g, 0.066 mol) was taken in ethanolic HCl (300 mL) and <strong>[14763-20-3]3-chlorophenyl hydrazine</strong> (9.43 g, 0.066 mol, 1 equivalent) was added. The reaction mixture was heated to reflux for 2 h. Progress of the reaction was monitored by TLC (20% ethyl acetate in n-hexane). On completion of the reaction, reaction contents were concentrated and the residue taken in water (200 mL). Basified the contents to a pH??12 with 1N NaOH solution and filtered the contents. Solid obtained was taken in ethyl acetate (200 mL), dried the contents over sodium sulfate and concentrated under reduced pressure to yield the required product as a red colored solid (12 g, 65%).

Reference： [1]Patent: WO2010/127855,2010,A1 .Location in patent: Page/Page column 157; 158
[2]Patent: WO2010/127856,2010,A1 .Location in patent: Page/Page column 121; 122
[3]Patent: US2012/46301,2012,A1 .Location in patent: Page/Page column 32
[4]Patent: US2012/115903,2012,A1 .Location in patent: Page/Page column 39
[5]Patent: WO2012/62463,2012,A1 .Location in patent: Page/Page column 86
[6]Patent: WO2012/62462,2012,A1 .Location in patent: Page/Page column 85
[7]Patent: US2012/115893,2012,A1 .Location in patent: Page/Page column 35
[8]Patent: WO2013/13815,2013,A1 .Location in patent: Page/Page column 109; 110
[9]Patent: US2013/29962,2013,A1 .Location in patent: Paragraph 0689

28
[ 1254716-82-9 ]
[ 14763-20-3 ]
[ 1254716-85-2 ]

Yield	Reaction Conditions	Operation in experiment
77%	With acetic acid; In 2-methoxy-ethanol; at 105℃; for 3h;	A mixture of step-b product (1.1 g, 5.164 mmol, 1 eq) and <strong>[14763-20-3]3-chlorophenyl hydrazine</strong> hydrochloride (1.84 g, 10.27 mmol, 2 eq) was taken in acetic acid (20 ml_), 2-methoxy EtOH (10 ml_) and the reaction mixture was heated at 1050C for 3 h. Solvent was evaporated and the residue was extracted with ethyl acetate (60 ml_). The organic layer washed with water (10 ml_), brine solution (10 ml), dried (Na2SO4), filtered and concentrated under reduced pressure to give a residue. Purification by column chromatography (silica gel: 100-200 mesh; eluent: ethyl acetate-petroleum ether (4:96)) afforded a pale brown semi solid (1.15g, 77%).
	In ethanol; acetic acid;Reflux;	To a stirred solution of step-b compound (40 g, 0.18 mol) in a 1 :1 mixture of acetic acid and ethanol (400 ml, 10 times) was dissolved at RT. To this reaction mixture 3- chlorophenylhydrazine (32.07 g, 1.2 eq) was added and stirred for about 10 minutes . The overall reaction was heated and reflux for 24 hrs. Progress of the reaction was monitored by TLC (10% ethyl acetate/hexane, 30% ethyl acetate/hexane). On completion of the reaction, Acetic acid and ethanol was distilled off under reduced pressure. Obtained crude was added to water (200 ml) and the extract was added to EtOAc (350 ml) to get separate layers. The organic layer obtained was dried over sodium sulfate and concentrated under reduced pressure. The crude compound brown colored liquid was obtained (33 g).
	With acetic acid; In ethanol; for 24h;Reflux;	Step c: To a stirred solution of step-b compound (40 g, 0.18 mol) in a 1:1 mixture of acetic acid and ethanol (400 ml, 10 times) was dissolved at RT. To this reaction mixture <strong>[14763-20-3]3-chlorophenylhydrazine</strong> (32.07 g, 1.2 eq) was added and stirred for about 10 minutes. The overall reaction was heated and reflux for 24 hrs. Progress of the reaction was monitored by TLC (10% ethyl acetate/hexane, 30% ethyl acetate/hexane). On completion of the reaction, Acetic acid and ethanol was distilled off under reduced pressure. Obtained crude was added to water (200 ml) and the extract was added to EtOAc (350 ml) to get separate layers. The organic layer obtained was dried over sodium sulfate and concentrated under reduced pressure. The crude compound brown colored liquid was obtained (33 g).

	With acetic acid; In ethanol; for 24h;Reflux;	Step c; To a stirred solution of step-b compound (40 g, 0.18 mol) in a 1 :1 mixture of acetic acid and ethanol (400 ml, 10 times) was dissolved at RT. To this reaction mixture 3- chlorophenylhydrazine (32.07 g, 1.2 eq) was added and stirred for about 10 minutes . The overall reaction was heated and reflux for 24 hrs. Progress of the reaction was monitored by TLC (10% ethyl acetate/hexane, 30% ethyl acetate/hexane). On completion of the reaction, Acetic acid and ethanol was distilled off under reduced pressure. Obtained crude was added to water (200 ml) and the extract was added to EtOAc (350 ml) to get separate layers. The organic layer obtained was dried over sodium sulfate and concentrated under reduced pressure. The crude compound brown colored liquid was obtained (33 g).
	With acetic acid; In ethanol; for 24h;Reflux;	To a stirred solution of step-b compound (40 g, 0.18 mol) in a 1 :1 mixture of acetic acid and ethanol (400 ml, 10 times) was dissolved at RT. To this reaction mixture 3- chlorophenylhydrazine (32.07 g, 1.2 eq) was added and stirred for about 10 minutes . The overall reaction was heated and reflux for 24 hrs. Progress of the reaction was monitored by TLC (10% ethyl acetate/hexane, 30% ethyl acetate/hexane). On completion of the reaction, Acetic acid and ethanol was distilled off under reduced pressure. Obtained crude was added to water (200 ml) and the extract was added to EtOAc (350 ml) to get separate layers. The organic layer obtained was dried over sodium sulfate and concentrated under reduced pressure. The crude compound brown colored liquid was obtained (33 g).
	In ethanol; acetic acid; for 24.1667h;	Step c: To a stirred solution of step-b compound (40 g, 0.18 mol) in a 1:1 mixture of acetic acid and ethanol (400 ml, 10 times) was dissolved at RT. To this reaction mixture <strong>[14763-20-3]3-chlorophenylhydrazine</strong> (32.07 g, 1.2 eq) was added and stirred for about 10 minutes. The overall reaction was heated and reflux for 24 hrs. Progress of the reaction was monitored by TLC (10% ethyl acetate/hexane, 30% ethyl acetate/hexane). On completion of the reaction, Acetic acid and ethanol was distilled off under reduced pressure. Obtained crude was added to water (200 ml) and the extract was added to EtOAc (350 ml) to get separate layers. The organic layer obtained was dried over sodium sulfate and concentrated under reduced pressure. The crude compound brown colored liquid was obtained (33 g).

Reference： [1]Patent: WO2010/127856,2010,A1 .Location in patent: Page/Page column 123; 124
[2]Patent: WO2010/127855,2010,A1 .Location in patent: Page/Page column 159; 160
[3]Patent: US2012/115903,2012,A1 .Location in patent: Page/Page column 41
[4]Patent: WO2012/62463,2012,A1 .Location in patent: Page/Page column 88
[5]Patent: WO2012/62462,2012,A1 .Location in patent: Page/Page column 88
[6]Patent: US2012/115893,2012,A1 .Location in patent: Page/Page column 37

29
[ 75-90-1 ]
[ 14763-20-3 ]
[ 116853-75-9 ]

Yield	Reaction Conditions	Operation in experiment
72%	In ethanol; for 5h;Reflux;	The aldehyde (K-I) (2 eq., 300 ml) obtained from kO1 and (3- chlorophenyl)hydrazine (K-IV) (1 eq., 20 g) were placed in EtOH (200 ml) and refluxed for 5 h. The solvent was removed under vacuum, the residue was purified by column chromatography (SiO2, hexane) and the product (25 g, 72 % yield) K-Il was obtained as a brown oil.
72%	In ethanol; for 5h;Reflux;	The aldehyde (K-I) (2 equiv., 300 mL) obtained from k01 and <strong>[14763-20-3](3-chlorophenyl)hydrazine</strong> (K-IV) (1 equiv., 20 g) were added to EtOH (200 mL) and refluxed for 5 h. The solvent was removed in vacuo, the residue was purified by column chromatography (SiO2, hexane) and the product (25 g, 72% yield) K-II was obtained as a brown oil.
72%	In ethanol; for 5h;Reflux;	Step k02: The aldehyde (K-I) (2 eq., 300 ml) obtained from k01 and <strong>[14763-20-3](3-chlorophenyl)hydrazine</strong> (K-IV) (1 eq., 20 g) were placed in EtOH (200 ml) and refluxed for 5 h. The solvent was removed under vacuum, the residue was purified by column chromatography (SiO2, hexane) and the product (25 g, 72% yield) K-II was obtained as a brown oil.

72%	In ethanol; for 5h;Reflux;	Step k02: The aldehyde (K-l) (2 eq., 300 ml) obtained from k01 and (3- chlorophenyl)hydrazine (K-IV) (1 eq., 20 g) were placed in EtOH (200 ml) and refluxed for 5 h. The solvent was removed under vacuum, the residue was purified by column chromatography (Si02, hexane) and the product (25 g, 72 % yield) K-ll was obtained as a brown oil.
72%	In ethanol; for 5h;Reflux;	The aldehyde (K-l) (2 eq., 300 ml) obtained from k01 and (3- chlorophenyl)hydrazine (K-IV) (1 eq., 20 g) were placed in EtOH (200 ml) and refluxed for 5 h. The solvent was removed under vacuum, the residue was purified by column chromatography (Si02, hexane) and the product (25 g, 72 % yield) K-ll was obtained as a brown oil.
72%	In ethanol; for 5h;Reflux;	The aldehyde (K-l) (2 equivalents, 300 mL) obtained from k01 and (3- chlorophenyl)hydrazine (K-IV) (1 equivalent, 20 g) were placed in ethanol (200 mL) and refluxed for 5 h. The solvent was removed under vacuum, the residue was purified by column chromatography (silica gel: 100-200 mesh, eluent: n-hexane) and the product (25 g, 72 %) K-ll was obtained as a brown oil.
72%	In ethanol; for 5h;Reflux;	The aldehyde (K-l) (2 equivalents, 300 mL) obtained from k01 and (3- chlorophenyl)hydrazine (K-IV) (1 equivalent, 20 g) were placed in ethanol (200 mL) and refluxed for 5 h. The solvent was removed under vacuum, the residue was purified by column chromatography (silica gel: 100-200 mesh, eluent: n-hexane) and the product (25 g, 72 %) K-ll was obtained as a brown oil.
72%	In ethanol; for 5h;Reflux;	The aldehyde (K-l) (2 equivalents, 300 mL) obtained from k01 and (3- chlorophenyl)hydrazine (K-IV) (1 equivalent, 20 g) were placed in ethanol (200 mL) and refluxed for 5 h. The solvent was removed under vacuum, the residue was purified by column chromatography (silica gel: 100-200 mesh, eluent: n-hexane) and the product (25 g, 72 %) K-ll was obtained as a brown oil.
	In ethanol; for 5h;Reflux;	Step k02:[0680]The aldehyde (K-I) (2 equivalents, 300 mL) obtained from k01 and <strong>[14763-20-3](3-chlorophenyl)hydrazine</strong> (K-IV) (1 equivalent, 20 g) were placed in ethanol (200 mL) and refluxed for 5 h. The solvent was removed under vacuum, the residue was purified by column chromatography (silica gel: 100-200 mesh, eluent: n-hexane) and the product (25 g, 72%) K-II was obtained as a brown oil.
25 g	In ethanol; for 5h;Reflux;	Step k02: The aldehyde (K-l) (2 equivalents, 300 mL) obtained from k01 and <strong>[14763-20-3](3-chlorophenyl)hydrazine</strong> (K-IV) (1 equivalent, 20 g) were placed in ethanol (200 mL) and refluxed for 5 h. The solvent was removed under vacuum, the residue was purified by column chromatography (silica gel: 100-200 mesh, eluent: n-hexane) and the product (25 g, 72 %) K-ll was obtained as a brown oil.

Reference： [1]Patent: WO2010/127856,2010,A1 .Location in patent: Page/Page column 81
[2]Patent: US2012/46301,2012,A1 .Location in patent: Page/Page column 29; 30
[3]Patent: US2012/115903,2012,A1 .Location in patent: Page/Page column 34
[4]Patent: WO2012/62463,2012,A1 .Location in patent: Page/Page column 75
[5]Patent: WO2012/62462,2012,A1 .Location in patent: Page/Page column 76
[6]Patent: WO2013/13815,2013,A1 .Location in patent: Page/Page column 107
[7]Patent: WO2013/68463,2013,A1 .Location in patent: Page/Page column 49
[8]Patent: WO2013/68464,2013,A1 .Location in patent: Page/Page column 51
[9]Bioorganic and Medicinal Chemistry Letters,2017,vol. 27,p. 4383 - 4388
[10]Patent: US2013/29962,2013,A1 .Location in patent: Paragraph 0680
[11]Patent: WO2013/68461,2013,A1 .Location in patent: Page/Page column 70

30
[ 87166-64-1 ]
[ 14763-20-3 ]
[ 1352147-07-9 ]

Yield	Reaction Conditions	Operation in experiment
81%	In ethanol for 72h; Reflux;

Reference： [1]Location in patent: experimental part Nofal, Zienab M.; Fahmy, Hoda H.; Zarea, Eman S.; El-Eraky, Wafaa [Acta poloniae pharmaceutica, 2011, vol. 68, # 4, p. 507 - 517]

31
[ 338966-53-3 ]
[ 14763-20-3 ]
[ 1391943-24-0 ]

Yield	Reaction Conditions	Operation in experiment
61%	With N-ethyl-N,N-diisopropylamine; In ethanol; for 2h;Reflux;	To a solution of 0.5047 g (1.1994 mmol) methyl 3-(2-chloro-6-fluorophenyl)-5-(1-(dimethylamino)-4,4,4-trifluoro-3-oxobut-1-en-2-yl)isoxazole-4-carboxylate in dry ethanol, were added 0.1790 g (0.9995 mmol) 3-Chlorophenylhydrazine and 0.17 mL (0.9995 mmol) N,N-Diisopropylethylamine (DIPEA). The reaction mixture was heated under reflux for 2 h.The product was isolated by using column chromatography (Petroleum ether:Diethyl ether 80:20) and 0.305 g (yield of theory: 61%) of clean product (example 11) was obtained. Result of LC/MS [M+H]+: 499.8; 1H NMR (DMSO-d6; CCl4): 3.66 (3H, s, CH3), 7.45-7.50 (1H, dd, CH-arom.), 7.55-7.58 (1H, d, CH-arom.), 7.65-7.77 (1H, d, CH-arom.), 7.65-7.77 (1H, dd, CH-arom. phenylhydrazine), 7.65-7.77 (1H, d, CH-arom. phenylhydrazine), 7.85 (1H, s, CH-arom phenylhydrazine), 8.56 (1H, s, 1-pyrazole)
61%	With N-ethyl-N,N-diisopropylamine; In ethanol; for 2h;Reflux;	To a solution of 0.5047 g (1.1994 mmol) methyl 3-(2-chloro-6-fluorophenyl)-5-(1-(dimethylamino)-4,4,4-trifluoro-3-oxobut-1-en-2-yl)isoxazole-4-carboxylate in dry ethanol, 0.1790 g (0.9995 mmol) 3-Chlorophenylhydrazine and 0.17 mL (0.9995 mmol) N,N-Diisopropylethylamine (DIPEA) were added. The reaction mixture was heated under reflux for 2 h. The product was isolated by using column chromatography (Petroleum ether:Diethyl ether 80:20), and 0.305 g (yield of theory: 61%) of the pyrazolyl-isoxazole derivative were obtained. Result of LC/MS [M+H]+: 499.9; 1H NMR (DMSO-d6; CCl4): 3.66 (3H, s, CH3), 7.45-7.50 (1H, dd, CH-arom.), 7.55-7.58 (1H, d, CH-arom.), 7.65-7.77 (1H, d, CH-arom.), 7.65-7.77 (1H, dd, CH-arom. phenylhydrazine), 7.65-7.77 (1H, d, CH-arom. phenylhydrazine), 7.85 (1H, s, CH-arom phenylhydrazine), 8.56 (1H, s, 1-pyrazole)

Reference： [1]Patent: US2012/196861,2012,A1 .Location in patent: Page/Page column 15
[2]Patent: US2012/196862,2012,A1 .Location in patent: Page/Page column 15

32
[ 766-40-5 ]
[ 14763-20-3 ]
[ 41931-11-7 ]

Yield	Reaction Conditions	Operation in experiment
	Stage #1: Mucochloric acid; 3-chlorophenyl hydrazine In ethanol at 20℃; for 3h; Stage #2: With acetic acid In ethanol for 3h; Reflux;

Reference： [1]Urbano, Mariangela; Guerrero, Miguel; Zhao, Jian; Velaparthi, Subash; Roberts, Edward; Adrian Saldanha, S.; Chase, Peter; Hodder, Peter; Wang, Zhiwei; Civelli, Olivier; Schaeffer, Marie-Therese; Brown, Steven; Rosen, Hugh [Bioorganic and medicinal chemistry letters, 2012, vol. 22, # 23, p. 7135 - 7141,7]

33
[ 14763-20-3 ]
[ 77509-92-3 ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 2 steps 1: acetic acid; ethanol 2: trichlorophosphate / 4 h / 90 °C

Reference： [1]Thumar, Nilesh J.; Patel, Manish P. [Journal of Heterocyclic Chemistry, 2012, vol. 49, # 5, p. 1169 - 1178]

34
[ 615-79-2 ]
[ 14763-20-3 ]
[ 1175972-08-3 ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 2 steps 1: triethylamine / acetonitrile / 20 °C 2: methanol; potassium hydroxide / tetrahydrofuran / 20 °C

Reference： [1]Liu, Shu; Premnath, Padmavathy Nandha; Bolger, Joshua K.; Perkins, Tracy L.; Kirkland, Lindsay O.; Kontopidis, George; McInnes, Campbell [Journal of Medicinal Chemistry, 2013, vol. 56, # 4, p. 1573 - 1582]

35
[ 99-92-3 ]
[ 14763-20-3 ]
[ 1431629-37-6 ]
[ 1431629-38-7 ]

Yield	Reaction Conditions	Operation in experiment
68%; 21%		General procedure: The appropriate substituted phenylhydrazine (1a-g, 1.0 mmol) and substituted acetophenone (2a-f, 1.0 mmol) were mixed in ethanol (20 mL) and a few drops of glacial AcOH were added. The solution was heated under reflux at 80 C for 1-2 h. The solvents were evaporated in vacuo to give a solid that was added to polyphosphoric acid (PPA) (30 mL), and the mixture slowly heated to 120 C and kept at this temperature for a few hours until the reaction was complete (TLC monitoring). The mixture was allowed to cool and then poured into cold water (50 mL). The acidic solution was neutralised by the slow addition of 1 M NaOH (aq) and the solid precipitate of crude product was collected. Purification by column chromatography (hexane/ethyl acetate) gave the required product(s) (3a-q).

Reference： [1]Bioorganic and Medicinal Chemistry Letters,2013,vol. 23,p. 2671 - 2674

36
[ 14763-20-3 ]
[ 13939-06-5 ]
[ 405174-97-2 ]
[ 1443227-41-5 ]

Yield	Reaction Conditions	Operation in experiment
63%	With palladium diacetate; caesium carbonate; catacxium A; In 1,4-dioxane; at 140℃; for 1h;Microwave irradiation; Inert atmosphere;	General procedure: To a solution of 2-bromobenzaldehyde (1) (1.00 mmol) and phenylhydrazine (2) (1.00 mmol)in anhydrous 1,4-dioxane (2 mL) was added cesium carbonate (3.00 mmol) in a 2-5 mLcapacity microwave vial. The mixture was stirred and degassed with argon gas for 5 min. Tothis mixture were added Pd(OAc)2 (0.10 mmol) and di-1-adamantyl-n-butylphosphine (0.20mmol) under argon atmosphere, and purged with argon gas for 2 min and then molybdenumhexacarbonyl (2.50 mmol) was added and the vial was sealed and irradiated in microwave at140 C for 1 h. The vial was cooled to room temperature over a period of 10 min and filteredthrough Celite pad, washed with ethyl acetate (10 mL). The combined filtrate was concentrated in vacuo and the obtained residue was purified by flash column chromatography over 4 g SNAP cartridge by eluting with gradient of 20-40% ethyl acetate in hexane to afford2-phenylphthalazin-1(2H)-one (3) (60%).

Reference： [1]Tetrahedron Letters,2013,vol. 54,p. 3694 - 3696

37
[ 14763-20-3 ]
[ 57039-63-1 ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 2 steps 1: acetic acid / ethanol / 100 °C 2: 2,4,6-tripropyl-1,3,5,2,4,6-trioxatriphosphinane-2,4,6-trioxide / toluene / 120 °C
	Multi-step reaction with 2 steps 1: acetic acid / ethanol / 100 °C / Inert atmosphere 2: polyphosphoric acid / 120 °C / Inert atmosphere

Reference： [1]Lian, Xiao-Li; Lei, Hao; Quan, Xue-Jing; Ren, Zhi-Hui; Wang, Yao-Yu; Guan, Zheng-Hui [Chemical Communications, 2013, vol. 49, # 74, p. 8196 - 8198]
[2]Chen, Wei-Li; Wu, Si-Yi; Mo, Xue-Ling; Wei, Liu-Xu; Liang, Cui; Mo, Dong-Liang [Organic Letters, 2018, vol. 20, # 12, p. 3527 - 3530]

38
[ 14763-20-3 ]
[ 94-05-3 ]
[ 15001-08-8 ]

Yield	Reaction Conditions	Operation in experiment
	With acetic acid In water at 20℃; for 12h;

Reference： [1]Pandey, Garima; Bhowmik, Subhendu; Batra, Sanjay [Organic Letters, 2013, vol. 15, # 19, p. 5044 - 5047]

39
[ 1603907-36-3 ]
[ 14763-20-3 ]
[ 1603902-87-9 ]

Yield	Reaction Conditions	Operation in experiment
	With O-(benzotriazol-1-yl)-N,N,N',N'-tetramethyluronium tetrafluoroborate; N-ethyl-N,N-diisopropylamine; In dichloromethane; at 20℃; for 2h;	A1.5 (500 mg, 1.32 mmol) was mixed with <strong>[14763-20-3](3-chlorophenyl)hydrazine</strong> (285 mg,1.59 mmol) and DIEA (1.2 mL) in CH2Ch (IO mL). To this solution was added 0-(benzotriazol-I-yl)-N,N,N',N'-tetramethyluronium tetrafluoroborate (TBTU) ( 550 mg, I. 7Immol). The resulting reaction mixture was stirred at room temperature for 2 h then dilutedwith aq. sat. NaHC03. The mixture was extracted with CH2Ch and the organic mixture wasdried over sodium sulfate, filtered, and concentrated. The crude mixture was purified byflash column chromatography to give Compound G 1. MS (EI) for CzsHz4ClFzNsOz, found:500.I (MH+). Analytical HPLC, ret. time= I8.29 min, 97% purity.

Reference： [1]Patent: WO2014/62938,2014,A1 .Location in patent: Paragraph 0272

40
[ 97165-74-7 ]
[ 14763-20-3 ]
[ 1620949-33-8 ]

Yield	Reaction Conditions	Operation in experiment
75%	With acetic acid; In ethanol; for 18h;Reflux;	General procedure: In a 100mL round-bottomed flask were added: 2.6×10-3mol of the beta-diketohydrazone 4-(2-(2,4-dioxo pentane-3-yliden)hydrazine)benzonitrile, 0.60g; 30mL of ethanol, 5mL of glacial acetic acid, and substituted hydrazine, R-C6H4-NHNH2 (R=4-OCH3 1, 2.9×10-3mol, 0,53g; 4-CH3 2, 3×10-3mol, 0.50g; 4-H 3, 3.2×10-2mol, 3.51g; 4-F 4, 3.1×10-3mol, 0.50g; 4-Cl 5, 3.0×10-3, 0.53g; 4-CF3 6, 2.7×10-3mol, 0.48g; 4-CN 7, 3.1×10-3mol, 0.52g; 3-Cl 8, 3.0×10-3mol, 0.53g; 3-NO2 9, 2.9×10-3mol, 0.54g; 2-Cl 10, 3.0×10-3mol, 0.53g. and perfluorophenylhydrazine 11, 2.6×10-3mol, 0.51g. The reaction mixture was heated at reflux temperature stirring magnetically during 18h. For precipitation of each compound the mixture was cooled to -18C by 2h and by addition of around 25mL of water. The yellow-orange solids were filtered by suction, washed with abundant water and dried under vacuum at 40C by 24h. All compounds were recrystallized from ethanol/H2O mixtures of variable composition or pure ethanol, except compound 3 which was recrystallized from 1:1 THF/EtOH.

Reference： [1]Polyhedron,2014,vol. 81,p. 414 - 420

41
[ 77287-34-4 ]
[ 14763-20-3 ]
1-(3-chloromethylphenyl)-1H-1,2,4-triazole [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
78%	at 160℃; under 12929.0 Torr; for 0.166667h;Microwave irradiation; Sealed tube;	General procedure: To a dried microwave tube was added phenylhydrazine (108mg, 1 mmol) and formamide (0.82 mL, 20 mmol). The tube was sealed with a plastic microwave septum and then placed into the microwave cavity and irradiated at 160 C, 250 psi, and 230W for 10 min. After completion of reaction (TLC), the mixture was cooled to r.t.; distilled H2O (10 mL) was added, and the mixture extracted with EtOAc (3 × 10 mL). The combined organic extracts were dried over Na2SO4, filtered, and concentrated under reduced pressure. The crude product was purified by silica gel column chromatography using a mixture of n-hexane and EtOAc as eluent.

Reference： [1]Synlett,2015,vol. 26,p. 404 - 407

42
[ 85302-07-4 ]
[ 14763-20-3 ]
1-(3-chlorophenyl)-1,5,6,7-tetrahydro-4H-indazol-4-one [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
93%	With acetic acid; for 2h;Reflux;	General procedure: To a solution of compound 7 (3 g, 18 mmol) in a mixture ofethanol and acetic acid (2:1) (48 mL) or, for the synthesis of compounds8 e-g, only glacial acetic acid (30 mL) the suitable hydrazine(18 mmol) was added and the reaction mixture was heated underreflux for 2 h. Then, the reaction mixture was poured onto crushedice and the solid was filtered off, dried and purified by chromatography(DCM/AcOEt 9:1) as eluent.

Reference： [1]European Journal of Medicinal Chemistry,2015,vol. 102,p. 334 - 351

43
[ 16169-88-3 ]
[ 14763-20-3 ]
C₁₅H₁₃ClN₂ [ No CAS ]

Reference： [1]ACS Catalysis,2015,vol. 5,p. 5026 - 5030

44
[ 2469-99-0 ]
[ 14763-20-3 ]
[ 91587-54-1 ]

Yield	Reaction Conditions	Operation in experiment
	With sodium acetate; In ethanol;Reflux;	Example 17 Synthesis of 1-(3-Chlorophenyl)-3-methyl-1H-pyrazol-5-amine (CE280) Step 1: (3-Chlorophenyl)hydrazine (415 mg), 3-oxobutanenitrile (895 mg), and sodium acetate (415 mg) were dissolved in ethanol (20 mL). The solution was heated at reflux for overnight. The reaction mixture was concentrated and partitioned between ethyl acetate and water. The aqueous layer was extracted with ethyl acetate. The combined organic layers were dried and concentrated on a rotary evaporator.

Reference： [1]Patent: US2015/246923,2015,A1 .Location in patent: Paragraph 0449-0450

45
[ 40928-13-0 ]
[ 14763-20-3 ]
2-amino-4-chloro-N'-(3-chlorophenyl)benzohydrazide [ No CAS ]

Reference： [1]Journal of Organic Chemistry,2015,vol. 80,p. 12410 - 12419

46
[ 40928-13-0 ]
[ 14763-20-3 ]
(E)-6-chloro-3-((3-chlorophenyl)diazenyl)benzo[c]isoxazole [ No CAS ]

Reference： [1]Journal of Organic Chemistry,2015,vol. 80,p. 12410 - 12419

47
[ 14763-20-3 ]
[ 72126-54-6 ]
5-(2-(3-chlorophenyl)hydrazinyl)-6-methylpyrazine-2,3-dicarbonitrile [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
65%	With pyridine; In methanol; at 140℃; under 112.51100000000001 Torr; for 0.5h;Microwave irradiation;	Compound 2 is prepared by reaction of 3-chlorophenylbydrazine (3 mmol) with 5-chloro-6- methylpyrazine-2,3-dicarbonitrile (II, 1 mmol) in 3 mL of methanol and pyridine (1 mniol). The reaction is performed in a microwave reactor at the temperature 140C, pressure 15 kPa and an output of 120 W during 30 mm. After completing the reaction, product 2 was isolated and purified by column chromatography on silica gel (mobile phase: hexane / ethyl acetate 1:1), yield 65%, Analytical data for compound 2: Green-brown crystalline solid; Mp. = 177.0-177.8C; Elemental analysis calculated for C13H9C1N6 (m.w. 284.70): 54.84% C, 3.19% H, 29.52% N; found 54.95% C, 2.95% H, 29.54% N; JR (ATR-Ge, cm??): 3314 (-NH-), 3285 (- NH-), 2231 (-CN), 1599, 1549, 1485, 1430, 1398 (pyr); ?H-NMR (300 MHz, CDC13) 6 10.05 (IH, bs, NH), 8.46 (1H, bs, NH), 7.16 (1H, t, J=? 8.0 Hz, H5?), 6.89-6.71 (3H, m, HZ, H4?, H6?), 2.52 (3H, s, CH3); ?3C NMR (75 MI-fr, DMSO) 6 153.6, 149.9, 147.0, 133.9, 130.7, 130.0, 119.3, 118.8, 115.5, 114.8, 111.8, 111.2, 21.3; Lipophilicity: calc. value log P 2.63; experimental determined value log k 0. 2499.

Reference： [1]Patent: WO2016/95877,2016,A1 .Location in patent: Page/Page column 17

48
[ 21279-62-9 ]
[ 14763-20-3 ]
3-(2-(3-chlorophenyl)hydrazinyl)pyrazine-2-carboxamide [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
24%	With pyridine; In methanol; at 140℃; under 112.51100000000001 Torr; for 0.5h;Microwave irradiation;	Compound 8 is prepared by reaction of 3-chlorophenylhydrazine (3 mmol) with 3- chloropyrazine-2-carboxamide (ifi, 1 mmol) in 3 mL methanol and pyridine (1 mniol). The reaction is performed in a microwave reactor at the temperature 140C, pressure 15 kPa and an output of 120 W during 30 mm. After completing the reaction, product 8 was isolated and purified by column chromatography on silica gel (mobile phase: hexane I ethyl acetate 1:1), yield 24%. Analytical data for compound 8: Dark brown crystalline solid; Mp. = 119.5- 120.9C; Elemental analysis calculated for C11H10C1N50 (m.w. 263.68): 50.10% C, 3.82% H, 26.56% N; found 50.3 1% C, 3.7 1% H, 26,55% N; IR (ATR-Ge, cm?): 3445 (-NH-), 3253 (-CONH2), 1671 (-C=O), 1598, 1522, 1476, 1413 (pyr); 1H-NMR (300 MHz, CDC13) ?HNMR (300 MHz, CDCI3) 8.34 (2H, bs, NH2), 7.92 (2H, bs, H5, H6), 7.63 - 6.82 (4H, m,1-12?, H4?, H5?, 116?), 5.71 (211, bs, NH); ?3C NMR (75 MHz, DMSO) & 168,89, 152.20,146.20, 140.24, 134.40, 132.36, 129.72, 126.57, 122.94, 120.26, 118.52; Lipophilicity: caic.values log P 0.34; experimental determined values log k = 0.5898.

Reference： [1]Patent: WO2016/95877,2016,A1 .Location in patent: Page/Page column 20; 21

49
[ 62-53-3 ]
[ 14763-20-3 ]
[ 101-17-7 ]

Yield	Reaction Conditions	Operation in experiment
85%	With copper phthalocyanine; copper(II) sulfate; In methanol; at 15℃;	Aniline reaction flask was added 0.093 g (1 mmol), 3- chlorophenyl hydrazine 0.185g (1.3 mmol), CuPc 0.058 Ke (0.1 mmol), Cu (SO 4) 20.026 g (0.1 mmol) and 10 ml ofmethanol 15 C reaction; TLC until the reaction was followed completely finished; thecrude product after the reaction was subjected to column chromatography (petroleumether: ethyl acetate = 100: 1) to give the desired product (85% yield).
55%	With tetrabenzoporphyrinatocobalt(II); copper diacetate; In acetonitrile; at 0℃; for 13h;	General procedure: Into a 25 mL round-bottom flask, amine (2) (1 mmol), Cu(OAc)2 (0.02 g, 0.1 mmol) and acetonitrile (4 mL) were added, the mixture was stirred and cooled to 0 C. Then, CoPc (0.057 g, 0.1 mmol) was added, the solution of arylhydrazine (1) (2 mmol) in acetonitrile (2 mL) was added successively at a rate of 0.2 mmol per hour while stirring for 13 h in air. After completion of the reaction monitored by TLC analysis (developing solvent: ethyl acetate/petroleum ether (1:8)), the mixture was filtered, concentrated, and the residue was further purified by column chromatography using ethyl acetate/petroleum ether (1:100) as eluent to afford N-aryl amine 3.

Reference： [1]Patent: CN104262167,2016,B .Location in patent: Paragraph 0126-0129
[2]Tetrahedron,2016,vol. 72,p. 6477 - 6483

50
1-(4-aminophenyl)-3-[4-(benzyloxy)phenyl]prop-2-en-1-one [ No CAS ]
[ 14763-20-3 ]
4-[5-[4-(benzyloxy)phenyl]-1-(3-chlorophenyl)-1H-pyrazol-3-yl]aniline [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
89%	In ethanol; at 60℃;	General procedure: A mixture of 1-(4-aminophenyl)-3-[4-(benzyloxy)phenyl]prop-2-en-1-one (2, 5 mmol) and different aryl hydrazines (7.5 mmol) in 25 cm3 of ethanol was refluxed at 60 C for 3-7 h. The solution was cooled at room temperature and poured into ice cold water. The precipitate thus obtained was filtered, washed with water, dried, and recrystallizedfrom ethanol.

Reference： [1]Monatshefte fur Chemie,2016,vol. 147,p. 2017 - 2029

51
1-(2-chlorophenyl)-1H-1,2,3-triazole-4-carbonyl chloride [ No CAS ]
[ 14763-20-3 ]
1-(2-chlorophenyl)-N'-(3-chlorophenyl)-1H-1,2,3-triazole-4-carbohydrazide [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
70%	With triethylamine; In dichloromethane; at 20℃;	General procedure: A mixture of compound 5a-f (1 mmol) and SOCl2 (10 mL) wasstirred and refluxed for 2 h. Remaining SOCl2 was removed bydistillation under reduced pressure. After SOCl2 was completelyremoved, the residue was directly dissolved in anhydrous CH2Cl2(20 mL). The synthesis of substituted phenylhydrazines was performedaccording to protocols from the literature [24]. Appropriatesubstituted phenylhydrazine (1 mmol) and TEA (2.5 mmol) wasadded dropwise, and the mixture was stirred at r.t. for 1 h [25].The reaction mixture was washed with saturated salt water several times. The CH2Cl2 solution was collected and dried withanhydrous Na2SO4. Further purification was carried out with silicagel column chromatography using petroleum ether/EtOAc (2:1) asthe eluent. The final compounds 6a and 6ab-6fg were obtained.