Category: pyrazoles-derivatives

Application of 3920-50-1,Some common heterocyclic compound, 3920-50-1, name is Pyrazole-3-carboxaldehyde, molecular formula is C4H4N2O, traditional synthetic route has been very mature, but the traditional synthetic route has various shortcomings, such as complicated route, low yield, poor purity, etc, below Introduce a new synthetic route.

Reference Production Example 6-1 1-(hydroxymethyl)-3-formyl-1H-pyrazole The mixture of 0.96 g of 3-formyl-1H-pyrazole, 0. 60 g of paraformaldehyde and 0.3 ml of triethylamine was stirred at 100 °C for 5 hours. After the reaction mixture was cooled to room temperature, acetone was added to the reaction mixture. The mixture was filtered. The filterate was concentrated under reduced pressure to obtain 1.21 g of 1-(hydroxymethyl)-3-formyl-1H-pyrazole. The crude product was used for next process without purification. 1H-NMR(CDCl3,TMS,delta(ppm)):5.63(2H,s),6.84(1H,d),7.67(1H,d),9.96(1H,s)

The synthetic route of 3920-50-1 has been constantly updated, and we look forward to future research findings.

Reference:
Patent; Sumitomo Chemical Company, Limited; EP1710234; (2006); A1;,
Pyrazole – Wikipedia,
Pyrazoles – an overview | ScienceDirect Topics

Reference of 930-36-9, These common heterocyclic compound, 930-36-9, name is 1-Methylpyrazole, its traditional synthetic route has been very mature, but the traditional synthetic route has various shortcomings, such as complicated route, low yield, poor purity, etc, below Introduce a new synthetic route.

Under room temperature, the 1-methyl -1H-pyrazole (2.0g, 24.4 mmol) dissolved in THF in (30 ml). Under the protection of the nitrogen of the obtained mixture to lower the temperature to -78 C, then slowly dripping n-BuLi to the (10.72 ml, 26.8 mmol). Then the resulting mixture at -78 C stirring 2 hours, to room temperature, then the stirring is performed for 1 hour. Then to the reaction solution to maintain this temperature in drying CO2gas, approximately through 5 minutes. After stirring at room temperature, to 1 hours. To the obtained water is added in the mixture of (30 ml) the reaction quenching and diluting. The resulting mixture is extracted with methylene chloride. After acid aqueous phase precipitating a large amount of solid, filtered. The resulting filter cake is dried to obtain 1.5 g of white solid (yield: 48.8%).

Statistics shows that 1-Methylpyrazole is playing an increasingly important role. we look forward to future research findings about 930-36-9.

Reference:
Patent; CSPC Weisheng Pharmaceutical Technology (Shijiahuang) Co., Ltd.; Shi, Ying; Gao, Qingzhi; Mi, Yi; Wang, Xuliang; (129 pag.)CN105384739; (2016); A;,
Pyrazole – Wikipedia,
Pyrazoles – an overview | ScienceDirect Topics

Electric Literature of 632365-54-9, Each compound has different characteristics, and only by selecting the characteristics of the compound suitable for a specific situation can the compound be applied on a large scale. 632365-54-9, name is Methyl 5-amino-1H-pyrazole-3-carboxylate, This compound has unique chemical properties. The synthetic route is as follows.

With stirring, a mixture of 10 g (0.037 mol) of dimethyl(2-chloro-4-cyanophenyl)malonate, 5.2 g (0.037 mol) of methyl 5-amino-1H-pyrazole-3-carboxylate and 7.6 g (0.041 mol) of tri-n-butyl-amine was heated at 180 C. for 6 hours. The methanol released during the reaction was continuously distilled off. The reaction mixture was then concentrated under reduced pressure. This gave 12.8 g (100% of theory) of methyl 5,7-dihydroxy-6-(2-chloro-4-cyanophenyl)pyrazolo[1,5-a]pyrimidine-3-carboxylate. The product was used for further syntheses without additional purification.

The chemical industry reduces the impact on the environment during synthesis Methyl 5-amino-1H-pyrazole-3-carboxylate. I believe this compound will play a more active role in future production and life.

Reference:
Patent; Gebauer, Olaf; Gayer, Herbert; Heinemann, Ulrich; Herrmann, Stefan; Hillebrand, Stefan; Elbe, Hans-Ludwig; Ebbert, Ronald; Wachendorff-Neumann, Ulrike; Dahmen, Peter; Kuck, Karl-Heinz; US2005/187224; (2005); A1;,
Pyrazole – Wikipedia,
Pyrazoles – an overview | ScienceDirect Topics

Related Products of 25016-20-0, These common heterocyclic compound, 25016-20-0, name is 1-Methyl-1H-pyrazole-3-carboxylic acid, its traditional synthetic route has been very mature, but the traditional synthetic route has various shortcomings, such as complicated route, low yield, poor purity, etc, below Introduce a new synthetic route.

Example 238 Production of N-[5-({2-[(cyclopropylcarbonyl)amino]imidazo[1,2-b]pyridazin-6-yl}oxy)-2-fluorophenyl]-1-methyl-1H-pyrazole-3-carboxamide To a solution of 1-methyl-1H-pyrazole-3-carboxylic acid (115 mg, 0.92 mmol) in tetrahydrofuran (4.0 mL) were added N,N-dimethylformamide (20 muL, 0.26 mmol) and oxalyl chloride (80 muL, 0.92 mmol), and the mixture was stirred at room temperature for 30 min. The reaction mixture was added to a solution of N-[6-(3-amino-4-fluorophenoxy)imidazo[1,2-b]pyridazin-2-yl]cyclopropanecarboxamide (200 mg, 0.62 mmol) in N,N-dimethylacetamide (4.0 mL), and the mixture was stirred at room temperature for 2 hr. Saturated aqueous sodium hydrogencarbonate solution was added to the reaction mixture, and the mixture was extracted with ethyl acetate/tetrahydrofuran, washed with saturated brine, dried over anhydrous sodium sulfate, and filtrated. The solvent was evaporated under reduced pressure and ethanol (10 mL) was added to the residue. The mixture was stirred with heating at 75 C. and cooled to room temperature, and the precipitate was collected by filtration to give the title compound (144 mg, 54%) as a white powder. 1H-NMR (DMSO-d6, 300 MHz) delta 0.77-0.83 (4H, m), 1.87-1.97 (1H, m), 3.97 (3H, s), 6.77 (1H, d, J=2.4 Hz), 7.06-7.16 (2H, m), 7.36-7.43 (1H, m), 7.82-7.89 (2H, m), 7.95 (1H, s), 8.05 (1H, d, J=9.6 Hz), 9.59 (1H, s), 11.08 (1H, s).

Statistics shows that 1-Methyl-1H-pyrazole-3-carboxylic acid is playing an increasingly important role. we look forward to future research findings about 25016-20-0.

Reference:
Patent; TAKEDA PHARMACEUTICAL COMPANY LIMITED; US2009/137595; (2009); A1;,
Pyrazole – Wikipedia,
Pyrazoles – an overview | ScienceDirect Topics

Reference of 175137-46-9,Some common heterocyclic compound, 175137-46-9, name is 5-Cyclopropyl-1H-pyrazol-3-amine, molecular formula is C6H9N3, traditional synthetic route has been very mature, but the traditional synthetic route has various shortcomings, such as complicated route, low yield, poor purity, etc, below Introduce a new synthetic route.

A solution of 5-cyclopropyl-1H-pyrazol-3-amine (0.267 g, 2.17 mmol) and 2,4,6-trichloroquinazoline (0.432 g, 2.17 mmol) in dimethylformamide (DMF) (10 mL) was treated with EtN(i-Pr)2 (0.49 mL, 2.82 mmol) and stirred for 4 h at 0 C. The reaction mixture was poured over ice water. The solid was collected by filtration and dried in air to provide compound 5 without further purification [16]. The yield was 74.6%.

The synthetic route of 175137-46-9 has been constantly updated, and we look forward to future research findings.

Reference:
Article; Wu, Tianxiao; Pang, Yu; Guo, Jing; Yin, Wenbo; Zhu, Mingyue; Hao, Chenzhou; Wang, Kai; Wang, Jian; Zhao, Dongmei; Cheng, Maosheng; Molecules; vol. 23; 2; (2018);,
Pyrazole – Wikipedia,
Pyrazoles – an overview | ScienceDirect Topics

Related Products of 1353100-91-0, As we all know, there are many different methods for the synthesis of a compound, and people can choose the synthesis method that suits their own laboratory according to the actual situation. 1353100-91-0 name is Ethyl 3-bromo-1H-pyrazole-4-carboxylate, This compound is widely used in many fields, so it is necessary to find a new synthetic route. The downstream synthesis method of this compound is introduced below.

Concentrated sulfuric acid (0.45 mL, 4.8 mmol) was added to a mixture of ethyl 3-bromo-1H-pyrazole-4-carboxylate (1.0 g, 4.6 mmol) and tert-amyl alcohol (3.0 mL, 27 mmol). The reaction was heated to 100 C. for 2.5 hours. The reaction was then cooled to room temperature and left stirring overnight. The reaction was diluted with ethyl acetate and washed with water. The organic layer was dried over sodium sulfate, filtered, and concentrated to yield ethyl 3-bromo-1-tert-pentyl-1H-pyrazole-4-carboxylate (1.3 g) as a crude brown oil.

At the same time, in my other blogs, there are other synthetic methods of this type of compound, Ethyl 3-bromo-1H-pyrazole-4-carboxylate, and friends who are interested can also refer to it.

Reference:
Patent; Pfizer Inc; US2012/108619; (2012); A1;,
Pyrazole – Wikipedia,
Pyrazoles – an overview | ScienceDirect Topics

Application of 5952-93-2, In the next few decades, the world population will flourish. As the population grows rapidly and people all over the world use more and more resources, all industries must consider their environmental impact. 5952-93-2, name is Methyl 1-methyl-1H-pyrazole-4-carboxylate belongs to pyrazoles-derivatives compound, it is a common compound, a new synthetic route is introduced below.

General procedure: To a solution of methyl 1-(methylcarbamoyl)-1H-pyrazole-3- carboxylate, Example 395.1 (0.943 g, 5.15 mmol) in MeOH (10 mL, 247 mmol), was added hydrazine (0.236 mL, 10.30 mmol) at RT. The resulting mixture was stirred at RT for 24 h. The mixture was then concentrated in vacuo and the residue was dissolved in water (100 mL). The aqueous solution was lyophilized to give the title compound (943 mg). LCMS-ESI (pos.): 184.1 (M+H)+.

The synthetic route of Methyl 1-methyl-1H-pyrazole-4-carboxylate has been constantly updated, and we look forward to future research findings.

Reference:
Patent; AMGEN INC.; CHEN, Ning; CHEN, Xiaoqi; CHEN, Yinhong; CHENG, Alan C.; CONNORS, Richard V.; DEIGNAN, Jeffrey; DRANSFIELD, Paul John; DU, Xiaohui; FU, Zice; HARVEY, James S.; HEATH, Julie Anne; HEUMANN, Lars V.; HORNE, Daniel B.; HOUZE, Jonathan; KALLER, Matthew R.; KAYSER, Frank; KHAKOO, Aarif Yusuf; KOPECKY, David J.; LAI, Su-Jen; MA, Zhihua; MEDINA, Julio C.; MIHALIC, Jeffrey T.; NISHIMURA, Nobuko; OLSON, Steven H.; PATTAROPONG, Vatee; SWAMINATH, Gayathri; WANG, Xiaodong; WANSKA, Malgorzata; YANG, Kevin; YEH, Wen-Chen; (700 pag.)WO2018/97945; (2018); A1;,
Pyrazole – Wikipedia,
Pyrazoles – an overview | ScienceDirect Topics

Reference of 1120-82-7, The chemical industry reduces the impact on the environment during synthesis 1120-82-7, name is (1H-Pyrazol-1-yl)methanol, I believe this compound will play a more active role in future production and life.

To a Schlenk tube was added Cul (9.5 mg), Pd(Ph3P)2Cl2 (35 mg), compound A (1085) (188 mg, 0.5 mmol), TMS acetylene (98 mg, 1.0 mmol), DMF (2 mL), and Et3N (0.5 mL). The reaction mixture was heated at 80 C for 12 hours. The reaction mixture was cooled and treated with EtOAc and brine. The organic layer was separated, dried, and evaporated. The residue was chromatographed on silica gel to give the TMS intermediate. The TMS intermediate was treated with TBAF (0.6 mmol) in 2 mL dry THF for 15 min. The residue was chromatographed on silica gel to give compound C (115 mg, 17% yield). (1086) [0621] To a solution of (lH-pyrazol-l-yl)methanol (196 mg, 2 mmol) in DCM (2 mL) was added methanesulfonyl chloride (4 mmol). The mixture was stirred at 0 C for 10 minutes then Et3N (6 mmol) was slowly added. After stirring at r.t. for 30 min, all volatiles were removed. 3-(4-Hydroxy-l-oxoisoindolin-2-yl)piperidine-2,6-dione (520 mg, 2 mmol), KHC03 (400 mg, 4 mmol), KI (10 mg) and 4 mL CH3CN were added to the residue. The mixture was heated at reflux overnight. The residue was chromatographed on silica gel to give compound D (210 mg, 31% yield). (1087) [0622] To a solution of compound D (210 mg, 0.62 mmol) in acetic acid (4 mL) was added NIS (321 mg, 0.75 mmol). The reaction was stirred for 1 h prior to being concentrated. The residue was purified by HPLC to afford compound E (156 mg, 54%). ESI-MS: 481.05. (1088) [0623] To a Schlenk tube was added Cul (2 mg), Pd(Ph3P)2Cl2 (4 mg), compound C (1089) (20 mg, 0.06 mmol), compound E (28 mg, 0.06 mmol), DMF (2 mL), and Et3N (0.5 mL). The reaction mixture was heated at 80 C for 12 hours. The reaction mixture was cooled and treated with EtOAc and brine. The organic layer was separated, dried, and evaporated. The residue was subjected to HPLC purification to afford Cpd. No. 82 (25 mg, 64% yield). ESI-MS: 674.05.

In the field of chemistry, the synthetic routes of compounds are constantly being developed and updated. I will also mention this compound in other articles, (1H-Pyrazol-1-yl)methanol, other downstream synthetic routes, hurry up and to see.

Reference:
Patent; THE REGENTS OF THE UNIVERSITY OF MICHIGAN; WANG, Shaomeng; HU, Yang; QIN, Chong; XU, Fuming; HU, Jiantao; ZHOU, Bing; CHEN, Zhou; FERNANDEZ-SALAS, Ester; BAI, Longchuan; McEACHERN, Donna; (198 pag.)WO2018/52945; (2018); A1;,
Pyrazole – Wikipedia,
Pyrazoles – an overview | ScienceDirect Topics

Related Products of 5334-40-7, These common heterocyclic compound, 5334-40-7, name is 4-Nitro-1H-pyrazole-3-carboxylic acid, its traditional synthetic route has been very mature, but the traditional synthetic route has various shortcomings, such as complicated route, low yield, poor purity, etc, below Introduce a new synthetic route.

4-(morpholinomethyl)phenyl-1,2-diamine (2.3 g, 1.11 mmol),4-nitro-1H-pyrazole-3-carboxylic acid (1.57 g, 1 mmol),EDCl (2.13 g, 1.11 mmol) and HOBt (1.5 g, 1.11 mmol)Dissolved in dry DMF (25 mL) and stirred at rt overnight.The solvent was removed under reduced pressure, was added glacial acetic acid (40 mL), was heated to reflux for 3 hours.The solvent was removed under reduced pressure and purified by column (dichloromethane/methanol (v/v) = 10/1).Then wash with methanol (10 mL),Methanol-insoluble product as a yellow solid that is, to give the product (0.9g, 27percent).

The synthetic route of 5334-40-7 has been constantly updated, and we look forward to future research findings.

Reference:
Patent; Guangdong Dongyangguang Pharmaceutical Co., Ltd.; Liu Bing; Zhang Yingjun; Zhang Jiquan; Li Yanping; Yang Xueqi; Zhang Jiancun; Zheng Changchun; (91 pag.)CN104211692; (2019); B;,
Pyrazole – Wikipedia,
Pyrazoles – an overview | ScienceDirect Topics

Synthetic Route of 288148-34-5, As we all know, there are many different methods for the synthesis of a compound, and people can choose the synthesis method that suits their own laboratory according to the actual situation. 288148-34-5 name is 1-Methyl-1H-pyrazole-4-sulfonyl chloride, This compound is widely used in many fields, so it is necessary to find a new synthetic route. The downstream synthesis method of this compound is introduced below.

Reference Example 106; tert-butyl ( {4-fluoro-5- (2-fluoropyridin-3-yl) -1- [ (1-methyl- lH-pyrazol-4-yl) sulfonyl] -lH-pyrrol-3- yl }methyl) methylcarbamate; To a solution of tert-butyl { [4-fluoro-5- (2- fluoropyridin-3-yl) -lH-pyrrol-3-yl]methyl }methylcarbamate (324 mg) in tetrahydrofuran (20 itiL) was added sodium hydride (60% in oil, 121 mg) at room temperature and the mixture was stirred for 15 min. 15-Crown-5 (664 mg) was added dropwise and the mixture was stirred for 5 min. l-Methyl-lH-pyrazole-4- sulfonyl chloride (362 mg) was added, and the mixture was further stirred for 30 min. The reaction mixture was diluted with saturated aqueous sodium hydrogen carbonate, and extracted with ethyl acetate. The extract was washed with saturated brine, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The residue was purified by silica gel column chromatography (eluent: hexane-ethyl acetate=l:l) to give the title compound as a colorless oil (yield 460 mg, 98%) .1H-NMR (CDCl3) delta: 1.48(9H,s), 2.88(3H,s), 3.87(3H,s),4.27(2H,brs) , 7.21 (IH, d, J=4.9Hz) , 7.30 (IH, t, J=6.1) , 7.41(lH,br), 7.42(lH,s), 7.86 (IH, t, J=8. IHz) ,8.29 (lH,d, J=4.9Hz) .

At the same time, in my other blogs, there are other synthetic methods of this type of compound, 1-Methyl-1H-pyrazole-4-sulfonyl chloride, and friends who are interested can also refer to it.

Reference:
Patent; TAKEDA PHARMACEUTICAL COMPANY LIMITED; WO2008/108380; (2008); A2;,
Pyrazole – Wikipedia,
Pyrazoles – an overview | ScienceDirect Topics