Name: 5350-57-2|Benzophenone hydrazone|95%
Brand: Ambeed
SKU: A490182
Price: 11.0 USD
Availability: InStock
Rating: 97 (26 reviews)

1
[ 119-61-9 ]
[ 5350-57-2 ]

Yield	Reaction Conditions	Operation in experiment
100%	With hydrazine hydrate In ethanol for 12h; Heating;
100%	With hydrazine hydrate; acetic acid In ethanol at 100℃; for 21h; Inert atmosphere;
100%	With hydrazine hydrate In ethanol for 4h; Reflux;	3.1 Synthesis of compound 5 The mixture of compound 4 (2 mmol) and excess hydrazine hydrate was stirred for 4 hours under reflux conditions. After the reaction was completed, the solvent and the remaining hydrazine hydrate were removed by rotary evaporation to obtain compound 5 with a yield of 100%.

99%	With hydrazine hydrate In ethanol for 12h; Reflux; Schlenk technique;
95%	With hydrazine hydrate In toluene for 0.333333h; microwave irradiation;
95%	With toluene-4-sulfonic acid; hydrazine hydrate In ethanol at 70 - 80℃;
95%	With hydrazine hydrate In ethanol for 24h; Reflux;	2.2 Synthesis of compound B1 5 mmol of benzophenone and 0.5749 mL of 65% hydrazine monohydrate was dissolved in ethanol 10 mL and refluxed for 24 hrs, then allowed to cool room temperature. The resulting residue was extracted with ice water and dichloromethane. The separated organic phase was dried over anhydrous magnesium sulfate and then concentrated in a vacuum to give the compound B1. Color: White solid. Yield: 95%
94%	With hydrazine hydrate; acetic acid In ethanol for 24h; Reflux;
91%	With hydrazine hydrate; acetic acid In ethanol at 40℃; for 24h;	2 2.2 Synthesis of benzophenone hydrazone (BPH) BPH was synthesized via Schiff base reaction. BP (2.0g, 11.1mmol) was dissolved in ethanol (80mL) at 40°C, followed by addition of excess hydrazine monohydrate (3.6mL). Adding one drop of aceticacid as a catalyst before the mixture was stirred and refluxed for 24h. After cooling to room temperature, the crude product was concentrated and then dissolved in ethyl acetate. The product was purified by washing the solution with deionized water thrice. After the organic solvent was evaporated under reduced pressure, white power of BPH was obtained in 91% yield. 1H NMR (400MHz, CDCl3) δ (ppm): δ7.53-7.24 (10H, aromatic ring), 5.41 (s, 2H, -NH2). HR-MS (ESI) calculated for C13H13N2+ (M+H)+ 197.1073, found 197.1079. Elemental analysis calculated (%) for C13H12N2: C 79.56, H 6.16, N 14.27, found C 78.52, H 6.40, N 14.12.
91%	With hydrazine hydrate In ethanol for 36h;	Step 1 . Synthesis of compound (83) A mixture of 82 (31 .0g, 170.3mmol) and N2H42O (1 1 .29g, 238.4mmol) in EtOH (100mL) was stirred at boiling temperature for 36 h. The solvent was removed under reduced pressure, the residue was dissolved in CH2CI2 (200mL), washed with water (50mL), from aqua layer the product was extracted with CH2CI2 (2x30mL), the combined organic layers were dried under Na2SC>4, the solvent was removed under reduced pressure to provide the product 83 (Yield: 91 %, 30.4g).
90%	With hydrazine hydrate; acetic acid for 6h; Reflux;	General procedure for the synthesis of compounds 2aand 2b General procedure: Benzophenone or 4′-hydroxybenzophenone (1 mmol) wastaken in hydrazine hydrate (10 mL) and refluxed for 6 hcatalyzed by acetic acid (2 mL; Scheme1). Progress ofchemical reaction was periodically monitored by TLCanalysis. When the reaction completed, water was addeduntil precipitation. These precipitates were filtered and driedunder vacuum.
89%	With hydrazine hydrate; acetic acid In ethanol for 12h; Reflux;
89%	With hydrazine hydrate; acetic acid In ethanol for 12h; Reflux;
88.7%	With toluene-4-sulfonic acid; hydrazine hydrate In ethanol for 6.5h; Reflux;	Method B General procedure: Method B A mixture of ketone(10 mmol, 1.0 equiv), hydrazine hydrate (3.4 mL, 60 mmol, 6.0 equiv), and p-TsOH·H2O (82 mg, 0.39 mmol,0.04 equiv) in ethanol (5 mL) was heated at reflux for 6.5 hours. After coolingto room temperature, the reaction mixture was concentrated under reduced pressure.Brine was added to the residue. The resulting slurry was extracted with EtOAcfor three times. The organic layer was collected and dried over anhydrous Na2SO4.The drying agent was removed by filtration and the solvent was removed undervacuum. The crude product was dissolved in a mixture of toluene (5 mL) andacetic anhydride (1 mL) and heated at reflux for 3 hours. Thereaction mixture was cooled to room temperature and neutralized with asaturated solution of Na2CO3. The organic layer wascollected and dried over anhydrous Na2SO4. The dryingagent was removed by filtration and the solvent was removed in vacuum to givethe crude product. After purification by medium-pressurecolumn chromatography, the acetylhydrazone was obtained.
86%	With hydrazine In ethanol; water Inert atmosphere; Reflux;
85%	With hydrazine hydrate
85%	With hydrazine hydrate In water; butan-1-ol Reflux;
83%	With hydrazine hydrate; acetic acid In ethanol for 12h; Reflux; Inert atmosphere;
82%	With hydrazine hydrate In ethanol for 12h; Reflux;	1 Benzophenone hydrazone (VI). Benzophenone hydrazone (VI). A mixture of benzophenone (10 g, 54.9 mmol), hydrazine monohydrate (3.78 mL, 76.8 mmol) and absolute ethanol (20 mL) was refluxed for 12 h. The solvent was removed under reduced pressure and the crude product was recrystallized from absolute ethanol to afford (VI) as white needles (8.78 g, 82%). NMR (400 MHz, CDCb) δ 7.52-7.38 (m, 5H), 7.29-7.20 (m, 5H), 5.42 (br, 2H) ; 13C (101 MHz, CDCh) 5 149.1, 138.5, 133.1, 129.5, 128.9, 128.8, 128.2, 128.1, 126.5 ; HRMS (ESI) calcd for C13H13N2 [M+H]+ 197.107, found 197.107
82%	With hydrazine hydrate In ethanol for 12h; Reflux;	1 Example 1Benzophenone hydrazone (1). Benzophenone hydrazone (1). A mixture of benzophenone (10 g, 54.9 mmol), hydrazine monohydrate(3.78 mL, 76.8 mmol) and absolute ethanol (20 mL) was refluxed for 12 h. The solvent was removed underreduced pressure and the crude product was recrystallized from absolute ethanol to afford 1 as white needles(8.78 g, 82%). ‘H NMR (400 MHz, CDCI3) D 7.52-7.38 (m, 5H), 7.29-7.20 (m, 5H), 5.42 (br, 2H) ; ‘3C(101 MHz, CDCI3)EIEI 149.1, 138.5, 133.1, 129.5, 128.9, 128.8, 128.2, 128.1, 126.5 ;HRMS (ESI) calcd forC,3H,3N2 [M+H] 197.107, found 197.107
80%	With hydrazine hydrate In ethanol for 10h; Heating;
80%	With hydrazine hydrate; acetic acid In ethanol Reflux;
80%	With hydrazine hydrate; acetic acid In ethanol for 20h; Reflux;
80%	With hydrazine hydrate; acetic acid In ethanol Inert atmosphere; Reflux;
80%	With hydrazine hydrate In methanol for 24h; Reflux;
72%	With hydrazine hydrate In ethanol for 12h; Reflux;
68%	With hydrazine hydrate; acetic acid In ethanol for 18h; Reflux;
45%	With hydrazine hydrate In ethanol Reflux;
32%	With acetic acid; hydrazine In diethyl ether for 3h; Heating;
15%	With hydrazine hydrate In ethanol for 48h; Reflux;	38.38-1 Benzophenone (25 g, 137 mmol) was dissolved in ethanol (250 mL) and hydrazine monohydrate (13.7 g, 274 mmol) was added. The resulting solution was stirred for one day with reflux. Then, additional hydrazine monohydrate (13 g) was added and the resulting solution was stirred for one day with reflux. After the starting material, benzophenone, disappeared, the resulting solution was concentrated under reduced pressure to remove ethanol, diluted with ethyl acetate (500 mL), and washed with water (300 mL×2) and saline (200 mL). The organic layer was dehydrated with anhydrous sodium sulfate and concentrated under reduced pressure. The thus-obtained solid was filtered under reduced pressure to yield Compound XLVIII (20 g (75%)). The filtrate was recrystallized with ethyl acetate and hexane to yield Compound XLVIII (4 g (15%)).1H NMR (400 MHz, DMSO-d6) δ 7.557.17 (m, 10H), 6.20 (s, 2H)
15%	With hydrazine hydrate In ethanol for 48h; Reflux;	38-1 Benzophenone (25 g, 137 mmol) was dissolved in ethanol (250 mL) and hydrazine monohydrate (13.7 g, 274 mmol) was added. The resulting solution was stirred for one day with reflux. Then, additional hydrazine monohydrate (13 g) was added and the resulting solution was stirred for one day with reflux. After the starting material, benzophenone, disappeared, the resulting solution was concentrated under reduced pressure to remove ethanol, diluted with ethyl acetate (500 mL), and washed with water (300 mL x 2) and saline (200 mL). The organic layer was dehydrated with anhydrous sodium sulfate and concentrated under reduced pressure. The thus-obtained solid was filtered under reduced pressure to yield Compound XLVIII (20 g (75%)). The filtrate was recrystalized with ethyl acetate and hexane to yield Compound XLVIII (4 g (15%)). 1H NMR (400MHz, DMSO-d6 ) δ 7.55∼7.17(m, 10H), 6.20(s, 2H)
	With ethanol; hydrazine hydrate at 150℃; im Rohr;
	With ethanol; hydrazine
	With hydrazine In ethanol for 0.5h; Heating;
	With hydrazine hydrate for 24h; Heating;
	With hydrazine hydrate In ethanol Heating;
	With hydrazine hydrate; acetic acid In ethanol Reflux;
	With hydrazine hydrate In ethanol Reflux;
	With hydrazine hydrate In dichloromethane
	With hydrazine hydrate In ethanol
	With hydrazine hydrate In methanol at 80℃; for 3h; Sealed tube;
	With hydrogenchloride; hydrazine hydrate In ethanol; water for 12h; Reflux;	4.1.1.1 Step 1. Preparation of diarylmethanone hydrazone General procedure: Hydrazine monohydrate (85% purity, 18.2mL, 30mmol) was added to a solution of diarylmethanone (20mmol) in ethanol (20mL). Then, aqueous HCl (36.0-38.0%, 0.5mL) was added and the mixture was heated to reflux for 12h. After cooling to room temperature, the diarylmethanone hydrazone was precipitated as white needle-shaped crystal. Filtration of the crude mixture gave pure diarylmethanone hydrazone (82-94% yield) as white solid.
	With toluene-4-sulfonic acid; hydrazine hydrate In water at 75℃;
	With hydrazine hydrate In ethanol
	With hydrazine hydrate; acetic acid In ethanol for 12h; Reflux; Inert atmosphere;
	With hydrazine hydrate In ethyl acetate at 40℃; for 2.5h;	1-9 Example 1 The synthesis method of the compound includes:3.64 g of benzophenone and 10 ml of 50% hydrazine hydrate were refluxed in 100 ml of ethyl acetate at 40 ° C for 2.5 h.After the reaction was cooled to give crystals of benzophenone hydrazone;1.82g of manganese dioxide was added to the dry ethyl acetate solution of benzophenone hydrazone,Stir at a temperature of 30 ° C for 1.2 h,After the completion of the reaction, the ethyl acetate solvent was distilled off under reduced pressure at room temperature.Then the residue is redissolved in ethyl acetate, and the ethyl acetate solvent is distilled off again under reduced pressure to obtain diphenyldiazomethane;Diphenyldiazomethane was reacted with 1.8 g of methyl acrylate in ethyl acetate solvent at 50 ° C for 1.5 h.After the reaction, the ethyl acetate solvent was distilled off under reduced pressure at room temperature under reduced pressure.Recrystallization from 95% ethanol then gave the desired product 4.85 g of 2,2-diphenylcyclopropanecarboxylic acid methyl ester.The yield was 91%.
10 g	With hydrazine hydrate; acetic acid In ethanol for 3h; Reflux;
	With acetic acid; hydrazine In water Heating;
	With hydrazine hydrate; acetic acid In ethanol for 16h; Reflux;
	With hydrazine hydrate In ethanol for 14h; Reflux; Inert atmosphere;
	With hydrazine hydrate; acetic acid In ethanol for 16h; Inert atmosphere; Reflux;
	With hydrazine hydrate; acetic acid In ethanol for 16h; Reflux;

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2
[ 22118-12-3 ]
[ 5350-57-2 ]
[ 93623-82-6 ]

Yield	Reaction Conditions	Operation in experiment
53%	With sodium hydroxide In dichloromethane for 12h; Ambient temperature;

Reference： [1]Okawara, Tadashi; Kato, Rie; Furukawa, Mitsuru [Chemical and pharmaceutical bulletin, 1984, vol. 32, # 6, p. 2426 - 2429]

3
[ 5350-57-2 ]
[ 122889-11-6 ]
[ 98694-89-4 ]

Reference： [1]Synthesis,1985,vol. NO. 5,p. 513 - 515

4
[ 5350-57-2 ]
[ 101-81-5 ]
[ 1016-09-7 ]
[ 2235-01-0 ]

Yield	Reaction Conditions	Operation in experiment
1: 3 % Chromat. 2: 32 % Chromat. 3: 37%	With sodium methylate In methanol at 70℃; for 6.4h; C-anode, C-cathode, 4.4 F/mol, constant current 0.5 A, undivided cell;

Reference： [1]Chiba, Toshiro; Okimoto, Mitsuhiro; Nagai, Hiroshi; Takata, Yoshiyuki [Journal of Organic Chemistry, 1983, vol. 48, # 18, p. 2968 - 2972]

5
[ 5350-57-2 ]
[ 13097-01-3 ]

Reference： [1]Journal of the Chemical Society. Chemical communications,1982,p. 450 - 452
[2]Tetrahedron Letters,2016,vol. 57,p. 2390 - 2394
[3]Tetrahedron Letters,2016,vol. 57,p. 2390 - 2394

6
[ 5350-57-2 ]
[ 79-39-0 ]
[ 86456-50-0 ]

Reference： [1]Journal of Organic Chemistry,1983,vol. 48,p. 2968 - 2972

7
[ 7623-09-8 ]
[ 5350-57-2 ]
[ 79289-07-9 ]

Yield	Reaction Conditions	Operation in experiment
91%	With pyridine In dichloromethane for 0.25h; Heating;

Reference： [1]Taylor, Edward C.; Haley, Neil F.; Clemens, Robert J. [Journal of the American Chemical Society, 1981, vol. 103, # 26, p. 7743 - 7752]

8
[ 20312-37-2 ]
[ 5350-57-2 ]
[ 168069-99-6 ]

Yield	Reaction Conditions	Operation in experiment
85%	With [bis(acetoxy)iodo]benzene; iodine In dichloromethane 1.) -10 deg C, 2 h, 2.) room temp., 2 h;
70%	With [bis(acetoxy)iodo]benzene; iodine at -10℃;

Reference： [1]McLaren [Journal of Organic Chemistry, 1995, vol. 60, # 19, p. 6082 - 6084]
[2]Hu, Ming-Kuan; Yang, Fu-Chu; Chou, Chi-Cheun; Yen, Mao-Hsiung [Bioorganic and Medicinal Chemistry Letters, 1999, vol. 9, # 4, p. 563 - 568]

9
[ 5350-57-2 ]
[ 20615-64-9 ]
[ 107893-62-9 ]

Reference： [1]Monatshefte fur Chemie,1963,vol. 94,p. 1 - 15

10
[ 4132-86-9 ]
[ 5350-57-2 ]
2-Benzyloxycarbonylamino-propionic acid benzhydryl ester [ No CAS ]

Reference： [1]Tetrahedron Letters,1997,vol. 38,p. 1239 - 1240

11
[ 1119-46-6 ]
[ 5350-57-2 ]
5-Chloro-pentanoic acid benzhydryl ester [ No CAS ]

Reference： [1]Tetrahedron Letters,1997,vol. 38,p. 1239 - 1240

12
[ 5350-57-2 ]
[ 1460-16-8 ]
Cycloheptanecarboxylic acid benzhydryl ester [ No CAS ]

Reference： [1]Tetrahedron Letters,1997,vol. 38,p. 1239 - 1240

13
[ 5350-57-2 ]
[ 4441-63-8 ]
4-Cyclohexyl-butyric acid benzhydryl ester [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
75%	With aluminum oxide; Oxone; iodine In dichloromethane at 0℃; for 10.5h;

Reference： [1]Curini, Massimo; Rosati, Ornelio; Pisani, Emanuela; Cabri, Walter; Brusco, Stefano; Riscazzi, Massimiliano [Tetrahedron Letters, 1997, vol. 38, # 7, p. 1239 - 1240]

14
[ 106-39-8 ]
[ 5350-57-2 ]
[ 40594-87-4 ]

Yield	Reaction Conditions	Operation in experiment
97%	With sodium hydroxide;palladium diacetate; 2-(dicyclohexylphosphino)-2'-methylbiphenyl; In tert-Amyl alcohol; xylene; at 103℃; for 1h;	11.2 g of sodium hydroxide (1.4 eq; 0.28 mol), 38.29 g of 4-bromo-chlorobenzene (1 eq; 0.2 mol) and 39.4 g of benzophenone hydrazone (1 eq; 0.2 mol) in 180 ml of degassed tert-amyl alcohol are loaded into a 500 ml reactor surmounted by a condenser, a mechanical stirrer and a temperature sensor, and placed under an inert atmosphere.44.9 mg of palladium acetate (0.1 mol %; 0.0002 mol) and 145.6 mg of 2-dicyclohexylphosphino-2-methylbiphenyl (0.0004 mol) in 20 ml of degassed xylene are loaded into a 100 ml Schlenk tube equipped with a magnetic stirrer and placed under an inert atmosphere.After stirring for twenty minutes, the catalyst thus prepared is transferred into the reactor.After stirring at 103 C. for one hour, the reaction mixture is hydrolyzed with 100 ml of water and 100 ml of xylene are added.The organic phase is separated and concentrated under reduced pressure (approximately 8 mm of mercury).Crystallization from ethanol makes it possible to isolate the benzophenone N-p-chlorophenylhydrazone in the form of pale yellow crystals, with a yield of 97%.

Reference： [1]Journal of the American Chemical Society,1999,vol. 121,p. 10251 - 10263
[2]Advanced Synthesis and Catalysis,2005,vol. 347,p. 773 - 782
[3]Synthetic Communications,2006,vol. 36,p. 1123 - 1129
[4]Patent: US7557248,2009,B2 .Location in patent: Page/Page column 24
[5]Journal of the American Chemical Society,1998,vol. 120,p. 6621 - 6622
[6]RSC Advances,2014,vol. 4,p. 3364 - 3367
[7]Advanced Synthesis and Catalysis,2006,vol. 348,p. 23 - 39

15
[ 5350-57-2 ]
[ 402-43-7 ]
[ 210536-92-8 ]

Yield	Reaction Conditions	Operation in experiment
91%	With caesium carbonate In toluene at 90℃; for 8h;
83%	With palladium diacetate; caesium carbonate; 2,2'-bis-(diphenylphosphino)-1,1'-binaphthyl In toluene Heating;
81%	With palladium diacetate; 2,2'-bis-(diphenylphosphino)-1,1'-binaphthyl; sodium t-butanolate In toluene for 48h; Heating;

72%

With 1,4-diaza-bicyclo[2.2.2]octane; nickel(II) bromide dimethoxyethane; perixanthenoxanthene In N,N-dimethyl acetamide at 25℃; for 15h; Inert atmosphere; Irradiation; Schlenk technique; Sealed tube;

Reference： [1]Hartwig, John F. [Angewandte Chemie - International Edition, 1998, vol. 37, # 15, p. 2090 - 2093]
[2]Wagaw; Yang; Buchwald [Journal of the American Chemical Society, 1998, vol. 120, # 26, p. 6621 - 6622]
[3]Wagaw, Seble; Yang, Bryant H.; Buchwald, Stephen L. [Journal of the American Chemical Society, 1999, vol. 121, # 44, p. 10251 - 10263]
[4]Pezzetta, Cristofer; Folli, Andrea; Matuszewska, Oliwia; Murphy, Damien; Davidson, Robert W. M.; Bonifazi, Davide [Advanced Synthesis and Catalysis, 2021, vol. 363, # 20, p. 4740 - 4753]

16
[ 5350-57-2 ]
[ 1908-61-8 ]
[ 443964-59-8 ]

Yield	Reaction Conditions	Operation in experiment
87%	With tris-(dibenzylideneacetone)dipalladium⁽⁰⁾; tri-tert-butyl phosphine; sodium t-butanolate In toluene at 80℃; for 5h;

Reference： [1]Ortner, Birgit; Waibel, Reiner; Gmeiner, Peter [Angewandte Chemie - International Edition, 2001, vol. 40, # 7, p. 1283 - 1285]

17
[ 65007-00-3 ]
[ 5350-57-2 ]
[ 19848-68-1 ]

Reference： [1]Organic letters,2001,vol. 3,p. 1351 - 1354

18
[ 5350-57-2 ]
[ 20114-55-0 ]
[ 10019-24-6 ]
[ 68161-05-7 ]
[ 632-51-9 ]

Reference： [1]European Journal of Organic Chemistry,2004,p. 820 - 825

19
[ 5350-57-2 ]
[ 460-00-4 ]
1-(diphenylmethylene)-2-(4-fluorophenyl)hydrazine [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
91%	With sodium hydroxide; 2-(dicyclohexylphosphino)-2'-methylbiphenyl In tert-Amyl alcohol at 103℃; for 4h;
91%	Stage #1: 1-Bromo-4-fluorobenzene With sodium hydroxide In tert-Amyl alcohol Heating; Stage #2: benzophenone hydrazone With 2-(dicyclohexylphosphino)-2'-methylbiphenyl In tert-Amyl alcohol at 103℃; for 4h;
80%	With Pd(PAd<SUB>3</SUB>)(4-FC<SUB>6</SUB>H<SUB>4</SUB>)Br; triethylamine In water; toluene at 80℃; for 24h; Inert atmosphere; Glovebox;

65%	With bis(triphenylphosphine)nickel(II) chloride; sodium t-butanolate; 1,3-bis[2,6-diisopropylphenyl]imidazolium chloride In 1,4-dioxane at 50℃; for 5h; Inert atmosphere;
91 % Chromat.	With sodium hydroxide; 2-(dicyclohexylphosphino)-2'-methylbiphenyl In tert-Amyl alcohol Heating;
95 %Spectr.	With 1,4-diaza-bicyclo[2.2.2]octane; nickel(II) bromide dimethoxyethane; perixanthenoxanthene In N,N-dimethyl acetamide at 25℃; for 40h; Inert atmosphere; Irradiation; Schlenk technique; Sealed tube;

Reference： [1]Mauger, Christelle; Mignani, Gerard [Advanced Synthesis and Catalysis, 2005, vol. 347, # 6, p. 773 - 782]
[2]Mauger, Christelle; Mignani, Gerard [Synthetic Communications, 2006, vol. 36, # 8, p. 1123 - 1129]
[3]Lau, Sii Hong; Yu, Peng; Chen, Liye; Madsen-Duggan, Christina B.; Williams, Michael J.; Carrow, Brad P. [Journal of the American Chemical Society, 2020, vol. 142, # 47, p. 20030 - 20039]
[4]Wu, Wei; Fan, Xin-Heng; Zhang, Li-Peng; Yang, Lian-Ming [RSC Advances, 2014, vol. 4, # 7, p. 3364 - 3367]
[5]Buchwald, Stephen L.; Mauger, Christelle; Mignani, Gerard; Scholz, Ulrich [Advanced Synthesis and Catalysis, 2006, vol. 348, # 1-2, p. 23 - 39]
[6]Pezzetta, Cristofer; Folli, Andrea; Matuszewska, Oliwia; Murphy, Damien; Davidson, Robert W. M.; Bonifazi, Davide [Advanced Synthesis and Catalysis, 2021, vol. 363, # 20, p. 4740 - 4753]

20
[ 626-60-8 ]
[ 5350-57-2 ]
3-(2-(diphenylmethylene)hydrazinyl)pyridine [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
99%	With (R)-(-)-1-[(S)-2-(dicyclohexylphosphino)ferrocenyl]ethyl di-t-butylphosphine; sodium t-butanolate In 1,2-dimethoxyethane at 70℃; for 16h;

Reference： [1]Shen, Qilong; Shekhar, Shashank; Stambuli, James P.; Hartwig, John F. [Angewandte Chemie - International Edition, 2005, vol. 44, # 9, p. 1371 - 1375]

21
[ 5350-57-2 ]
[ 2845-89-8 ]
[ 210536-90-6 ]

Yield	Reaction Conditions	Operation in experiment
82%	With (R)-(-)-1-[(S)-2-(dicyclohexylphosphino)ferrocenyl]ethyl di-t-butylphosphine; sodium t-butanolate In 1,2-dimethoxyethane at 80℃;

Reference： [1]Shen, Qilong; Shekhar, Shashank; Stambuli, James P.; Hartwig, John F. [Angewandte Chemie - International Edition, 2005, vol. 44, # 9, p. 1371 - 1375]

22
[ 5350-57-2 ]
[ 50597-88-1 ]
[ 863727-65-5 ]

Yield	Reaction Conditions	Operation in experiment
95%	With 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene; sodium t-butanolate In toluene at 20 - 85℃; for 12h;	B.1 To a stirred, degassed suspension of 3-iodo-4-methoxytoluene (19.84 g, 80 mmol, 1 equiv), benzophenone hydrazone (17.99 g, 88 mmol, 1.1 equiv), Xantphos (93 mg, 0.16 mmol, 0.2 mol %), and Pd(OAc)2 (36 mg, 0.16 mmol, 0.2 mol %) in anhydrous toluene (96 mL) was added NaOtBu (11.09 g, 112 mmol, 1.4 equiv) in one portion at rt. The mixture was heated to 85° C. and stirred for 12 h. The reaction mixture was cooled, diluted with 200 mL EtOAc and 100 mL water, then the layers separated. The insoluble Pd residues were separated as the aqueous layer was removed. The organic phase was washed 2×100 mL water, then brine, and dried over Na2SO4. The solution was concentrated under reduced pressure, giving an orange-yellow solid. The solid was triturated in 50 mL MeOH, collected via filtration, and washed with 50 mL MeOH. Drying under suction gave the title compound as a yellow solid (24.16 g, 95% yield). 1H NMR (400 MHz, DMSO-d6) δ 2.25 (s, 3H), 3.56 (s, 3H), 6.53 (dd, 1H), 6.72 (d, 1H), 7.30 (m, 6H), 7.46 (d, 2H), 7.56 (m, 1H), 7.62 (m, 2H), 7.79 (s, 1H). ES-MS m/z 317.1 (MH+); HPLC RT (min) 4.26.

Reference： [1]Current Patent Assignee: BAYER AG - US2005/192294, 2005, A1 Location in patent: Page/Page column 10-11

23
[ 5350-57-2 ]
[ 3262-72-4 ]
[ 16357-59-8 ]
[ 121415-68-7 ]

Yield	Reaction Conditions	Operation in experiment
24.5 g (64%)	In hexane; dichloromethane; ethyl acetate;	EXAMPLE 1 N-(t-Butyloxycarbonyl)-L-serine-2-(diphenylmethylene)hydrazide; (3a) A solution of 20.0 g (0.10 mole) of t-butyloxycarbonyl-L-serine, 19.6 g (0.10 mole) of benzophenone hydrazone, and 24.7 g of 2-ethoxy-1(2H)-quinolinecarboxylic acid ethyl ester in 250 ml of methylene chloride was stirred at room temperature for 16 hours. The solution was extracted with successive 100 ml portions of 1N hydrochloric acid, water, saturated sodium bicarbonate solution, water and brine, then dried over magnesium sulfate. The solvent was evaporated in vacuo and the resulting syrup was dissolved in ethyl acetate and crystallized by the addition of hexane to afford 24.5 g (64%) of product, mp 150.0-152.5 C.

Reference： [1]Patent: US4808579,1989,A

24
[ 17228-69-2 ]
[ 5350-57-2 ]
[ 913839-70-0 ]

Reference： [1]Patent: WO2006/114213,2006,A1 .Location in patent: Page/Page column 42
[2]ChemMedChem,2018,vol. 13,p. 988 - 1003

25
[ 3430-17-9 ]
[ 5350-57-2 ]
[ 928264-09-9 ]

Yield	Reaction Conditions	Operation in experiment
62.4%	With sodium t-butanolate In toluene at 95℃;	7.1 Example 7Preparation of 2-{r3-ethyI-4-(6-methoxypyridin-3-yI)-l-(3-methyIpyridin-2-yI)-lH- pyrazol-5-vnamino}-5-(trifluoromethoxy)benzoic acidStep 1: Preparation of diphenylmethanone (3-methylpyridin-2-yl)hydrazone; A mixture of 2-bromo-3 -methyl pyridine (10.76 g, 62.55 mmol), benzophenone hydrazone (11.16 g, 56.87 mmol) and Xantphos (1.65 g, 2.84 mmol) in toluene (100 mL) was degassed by passing nitrogen through for 0.5 h. To the mixture was added sodium t-butoxide (13.12 g, 136.48 mmol) followed by Pd(OAc)2 (0.64 g, 2.84 mmol) and the mixture was stirred at 950C overnight. Some red solid was observed. The reaction mixture was concentrated to a third of its original volume. The red solid formed was collected by filtration, washed with hexanes, then dried under vacuum to give the desired compound (10.20 g, 62.4%). 1H NMR (400 MHz, DMSO-d6) δ 7.98-7.96 (IH, d, J = 8 Hz), 7.90 (lH,s), 7.66-6.76 (1 IH, m), 6.79-6.76 (IH, t, J = 4.5 Hz), 2.20 (3H,S); LC-MS m/z 288.1 (MH+), HPLC RT (min) 2.38 {method (A)}.

Reference： [1]Current Patent Assignee: BAYER AG - WO2007/27842, 2007, A1 Location in patent: Page/Page column 52

26
[ 407-20-5 ]
[ 5350-57-2 ]
[ 940012-08-8 ]

Yield	Reaction Conditions	Operation in experiment
81%	With 4,5-bis(diphenylphos4,5-bis(diphenylphosphino)-9,9-dimethylxanthenephino)-9,9-dimethylxanthene; sodium t-butanolate;palladium diacetate; In toluene; at 85℃; for 17h;	To a degassed solution of <strong>[407-20-5]5-bromo-3-fluoropyridine</strong> (9.2 g, 50.7 mmol), benzophenone hydrazone (11.2 g, 55.8 mmol), and 9,9-dimethyl-4,5-bis(dephenylphospino)xanthene (296 mg, 0.51 mmol) in toluene (80 mL) was added sodium te/t-butoxide (6.8 g, 71.0 mmol) and palladium (II) acetate (114 mg, 0.51 mmol). The reaction mixture was stirred at 85 0C under nitrogen for 17 h, cooled to rt, and then partitioned between EtOAc and water. The organic layer was washed with water and brine, dried (Na2SO4), filtered and concentrated under reduced pressure. The residue was triturated using a mixture of hexanes and methanol to give the title compound as a solid (12 g, 81 % yield). LC-MS [M+H]+ = 292.5, RT = 3.40 min.

Reference： [1]Patent: WO2007/64872,2007,A2 .Location in patent: Page/Page column 84

27
[ 5350-57-2 ]
[ 513-81-5 ]
[ 959624-02-3 ]

Yield	Reaction Conditions	Operation in experiment
90%	With 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene In dichloromethane at 23℃; for 24h;

Reference： [1]Johns, Adam M.; Liu, Zhijian; Hartwig, John F. [Angewandte Chemie - International Edition, 2007, vol. 46, # 38, p. 7259 - 7261]

28
[ 34784-04-8 ]
[ 5350-57-2 ]
[ 1031440-52-4 ]

Yield	Reaction Conditions	Operation in experiment
86%	With 2,2'-bis-(diphenylphosphino)-1,1'-binaphthyl; sodium t-butanolate; In toluene; at 85℃; for 4h;	To a suspension of <strong>[34784-04-8]<strong>[34784-04-8]5-bromoisoquinolin</strong>e</strong> (200 mg, 0.96 mmol), benzhydrylidene-hydrazine (189 mg, 0.96 mmol), palladium diacetate (2.2 mg, 0.0096 mmol) and 2,2'-bis(diphenylphosphino)-1 ,1 '-binaphthyl (BINAP, 6 mg, 0.0096 mmol) in dry toluene (1 ml_), sodium tert-butoxide (130 mg, 1.34 mmol) was added and the mixture was heated at 85 0C for 4 hours. The mixture, cooled to room temperature, was filtered over celite and the pad was washed with diethylether. The solvent was evaporated under vacuum and the residue was purified by flash chromatography with hexane/ethylacetate 7/3 as eluant, affording 268 mg of the title compound (86% yield).1 H NMR (400 MHz, DMSO-D6) delta ppm 7.35 (d, J=6.10 Hz, 1 H) 7.38 - 7.45 (m, 3 H)7.48 - 7.52 (m, 2 H) 7.57 - 7.74 (m, 7 H) 7.88 (dd, J=7.44, 1.10 Hz, 1 H) 8.39 (d, J=5.97Hz, 1 H) 8.76 (s, 1 H) 9.24 (s, 1 H).[M+H]+= 324

Reference： [1]Patent: WO2008/104475,2008,A1 .Location in patent: Page/Page column 25
[2]Patent: WO2008/65054,2008,A1 .Location in patent: Page/Page column 64

29
[ 50998-17-9 ]
[ 5350-57-2 ]
[ 1020173-84-5 ]

Yield	Reaction Conditions	Operation in experiment
20%		Example B28 In toluene (8 mL) was placed 1-(diphenylmethylene)hydrazine (1.00 g, 5.10 mmol), palladium acetate (10.4 mg, 0.0464 mmol) and 2-(diphenylphosphino)-1-(2-(diphenylphosphino)naphthalen-1-yl)naphthalene (44 mg, 0.0696 mmol) and the reaction was stirred at 100 C. under Ar for 5 min and then cooled to RT. To this dark purple solution was added <strong>[50998-17-9]<strong>[50998-17-9]6-bromoquinoxalin</strong>e</strong> (970 mg, 4.64 mmol), sodium t-butoxide (624 mg, 6.50 mmol) and toluene (2 mL). The reaction was placed under Ar and warmed to 100 C. for 5 hrs, cooled to RT and stirred overnight. The reaction was diluted with ether (50 mL) and water (30 mL) and filtered through a Celite pad. The pad was washed with ether (20 mL) and water (20 mL). The combined organic layers were washed with brine (50 mL), dried (Na2SO4), concentrated in vacuo and purified by chromatography (ethyl acetate/hexanes) to give 1-(diphenylmethylene)-2-(quinoxalin-6-yl)hydrazine (305 mg, 20% yield) as a bright yellow foam. 1H NMR (300 MHz, DMSO-d6) delta 7.35-7.41 (m, 5H), 7.51-7.53 (m, 2H), 7.58-7.65 (m, 3H), 7.75 (s, 1H), 7.89 (s, 2H), 8.61 (s, 1H), 8.74 (s, 1H), 9.60 (s, 1H); MS (ESI) m/z: 325.0 (M+H+).
20%	With palladium diacetate; 2,2'-bis-(diphenylphosphino)-1,1'-binaphthyl; sodium t-butanolate; In toluene; at 100℃; for 5h;Inert atmosphere;	In toluene (8 mL) was placed 1- (diphenylmethylene)hydrazine (1.00 g, 5.10 mmol), palladium acetate (10.4 mg, 0.0464 mmol) and 2-(diphenylphosphino)- 1 -(2-(diphenylphosphino)naphthalen- 1 -yl)naphthalene (44 mg, 0.0696 mmol) and the reaction was stirred at 100 C under Ar for 5 min and then cooled to RT. To this dark purple solution was added <strong>[50998-17-9]<strong>[50998-17-9]6-bromoquinoxalin</strong>e</strong> (970 mg, 4.64 mmol), sodium t-butoxide (624 mg, 6.50 mmol) and toluene (2 mL). The reaction was placed under Ar and warmed to 100 C for 5 hrs, cooled to RT and stirred overnight. The reaction was diluted with ether (50 mL) and water (30 mL) and filtered through a Celite pad. The pad was washed with ether (20 mL) and water (20 mL). The combined organic layers were washed with brine (50 mL), dried (Na2SC>4), concentrated in vacuo and purified by chromatography (ethyl acetate/hexanes) to give l-(diphenylmethylene)-2- (quinoxalin-6-yl)hydrazine (305 mg, 20% yield) as a bright yellow foam. FontWeight="Bold" FontSize="10" H NMR (300 MHz, DMSO-i/e) delta 7.35-7.41 (m, 5 H), 7.51-7.53 (m, 2 H), 7.58-7.65 (m, 3 H), 7.75 (s, 1 H), 7.89 (s, 2 H), 8.61 (s, 1 H), 8.74 (s, 1 H), 9.60 (s, 1 H); MS (ESI) m/z: 325.0 (M+H+).

Reference： [1]Patent: US2008/90856,2008,A1 .Location in patent: Page/Page column 48
[2]Patent: WO2013/36232,2013,A2 .Location in patent: Paragraph 00347

30
[ 5350-57-2 ]
[ 450-89-5 ]
Diphenylmethanone (4-fluoro-2-methoxyphenyl)hydrazone [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	With sodium t-butanolate;tris-(dibenzylideneacetone)dipalladium(0); johnphos; In toluene; at 80℃;	Diphenylmethanone (4-fluoro-2-methoxyphenyl)hydrazone A mixture of <strong>[450-89-5]2-chloro-5-fluoroanisole</strong> (0.52 ml, 4.10 mmol), benzophenone hydrazone (0.98 g, 5.00 mmol), sodium-tert-butoxide (561 mg, 5.80 mmol), in toluene (8.0 ml) was charged with Pd2(dba)3 (77.0 mg, 0.08 mmol) and 2-(di-t-butylphosphino)biphenyl (50.0 mg, 0.17 mmol) and heated to 80 C. under argon. The mixture was stirred overnight and checked with LCMS and TLC. The mixture was allowed to cool to room temperature and the reaction mixture was diluted with EtOAc (20 ml) and filtered. Material was used crude in the next step.

Reference： [1]Patent: US2009/12077,2009,A1 .Location in patent: Page/Page column 33

31
[ 5350-57-2 ]
[ 1435-48-9 ]
benzophenone N-5-chloro-2-fluorophenylhydrazone [ No CAS ]
benzophenone N-3-chloro-4-fluorophenylhydrazone [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
85%Chromat.; 15%Chromat.	With sodium hydroxide;palladium diacetate; 4,5-bis(diphenylphos4,5-bis(diphenylphosphino)-9,9-dimethylxanthenephino)-9,9-dimethylxanthene; In tert-Amyl alcohol; at 103℃; for 12h;	448 mg of milled sodium hydroxide (1.4 eq; 0.0112 mmol), 1.32 g of <strong>[1435-48-9]1,3-dichloro-4-fluorobenzene</strong> (1 eq; 0.008 mol) and 1.57 g of benzophenone hydrazone (1 eq; 0.008 mol) in 6 ml of degassed tert-amyl alcohol are loaded into a 20 ml reactor surmounted by a condenser, a mechanical stirrer and a temperature sensor, and placed in an inert atmosphere.8.95 mg of palladium acetate (0.001 mol %; 0.00004 mol) and 46.3 mg of 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene (0.0008 mol) in 2 ml of degassed tert-amyl alcohol are loaded into a 100 ml Schlenk tube equipped with a magnetic stirrer and placed under an inert atmosphere.After stirring for twenty minutes, the catalyst thus prepared is transferred into the reactor.After stirring at 103 C. for 12 hours, the conversion of the <strong>[1435-48-9]1,3-dichloro-4-fluorobenzene</strong> is complete and a benzophenone N-5-chloro-2-fluorophenylhydrazone yield of 85% (accompanied by 15% of benzophenone N-3-chloro-4-fluorophenylhydrazone) is measured by gas chromatography in the presence of an internal standard (hexacosane).

Reference： [1]Patent: US7557248,2009,B2 .Location in patent: Page/Page column 27

32
[ 5350-57-2 ]
[ 60811-21-4 ]
benzophenone N-3-chloro-4-fluorophenylhydrazone [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
83%	With sodium hydroxide;palladium diacetate; 4,5-bis(diphenylphos4,5-bis(diphenylphosphino)-9,9-dimethylxanthenephino)-9,9-dimethylxanthene; In tert-Amyl alcohol; at 103℃; for 12h;	448 mg of milled sodium hydroxide (1.4 eq; 0.0112 mmol), 1.67 g of <strong>[60811-21-4]4-bromo-2-chloro-1-fluorobenzene</strong> (1 eq; 0.008 mol) and 1.57 g of benzophenone hydrazone (1 eq; 0.008 mol) in 6 ml of degassed tert-amyl alcohol are loaded into a 20 ml reactor surmounted by a condenser, a mechanical stirrer and a temperature sensor, and placed under an inert atmosphere.8.95 mg of palladium acetate (0.001 mol %; 0.00004 mol) and 46.3 mg of 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene (0.0008 mol) in 2 ml of degassed tert-amyl alcohol are loaded into a 100 ml Schlenk tube equipped with a magnetic stirrer and placed under an inert atmosphere.After stirring for twenty minutes, the catalyst thus prepared is transferred into the reactor.After stirring at 103 C. for 12 hours, the conversion of the 4 bromo-2-chloro-1-fluorobenzene is complete.The reaction mixture is hydrolyzed with 10 ml of water and the organic phase is separated.Direct crystallization from tert-amyl alcohol makes it possible to isolate the corresponding benzophenone N-3-chloro-4-fluorophenylhydrazone with a yield of 83%.

Reference： [1]Patent: US7557248,2009,B2 .Location in patent: Page/Page column 26

33
[ 5350-57-2 ]
[ 42872-83-3 ]
[ 1219024-60-8 ]