Category: pyrazoles-derivatives

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. 37687-24-4, name is Diethyl 3,5-pyrazoledicarboxylate, This compound has unique chemical properties. The synthetic route is as follows., Safety of Diethyl 3,5-pyrazoledicarboxylate

Example 4: ethyl 4-hydroxy-6-methyl-pyrazolo[l,5-a]pyrazine-2-carboxylate (0257) l-Chloropropan-2-one (10.5 kg, 113 mol) was added slowly at room temperature (0258) (exothermic) to a suspension of diethyl lH-pyrazole-3,5-dicarboxylate (20 kg, 94.2 mol) and cesium carbonate (30.7 kg, 94.2 mol) in acetone (200 1). The reaction mixture was stirred for 1.5 hours, filtred and the precipitate was washed with acetone. Acetone was distilled off from the filtrate at 60 C to obain a volume of 60-90 1, DMSO (85 1) was added and the distillation was continued until acetone was completely removed. (0259) Ammonium acetate (14.5 kg, 188 mol) was added at room temperature. The reaction mixture was stirred at 80 C for 18 hours, cooled to 60 C and water (290 1) was slowly added. The suspension was stirred 2 hours at 0-5 C. The precipitate was filtered off, washed with water and dried at 70 C under high vacuum affording ethyl 4-hydroxy-6- methyl-pyrazolo[l,5-a]pyrazine-2-carboxylate (16.8 kg, 80.6%) as beige crystals. (0260) 1H-NMR (600 MHz, DMSO-d6): 11.51 (s, 1H), 7.62 (s, 1H), 7.32 (s, 1H), 4.33 (q, 2H), 2.14 (s, 3H), 1.32 (t, 3H); MS(ISP): m/e = 222.09 (M+H+).

According to the analysis of related databases, 37687-24-4, the application of this compound in the production field has become more and more popular.

Reference:
Patent; F. HOFFMANN-LA ROCHE AG; HOFFMANN-LA ROCHE INC.; DOTT, Pascal; FEYEN, Fabian; HILDBRAND, Stefan; HOFFMANN, Ursula; HOFFMANN-EMERY, Fabienne; MEIER, Roland; MOINE, Gerard; REGE, Pankaj; WUITSCHIK, Georg; (64 pag.)WO2017/186668; (2017); A1;,
Pyrazole – Wikipedia,
Pyrazoles – an overview | ScienceDirect Topics

Reference of 25016-11-9, 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. 25016-11-9, name is 1-Methyl-1H-pyrazole-4-carbaldehyde, This compound has unique chemical properties. The synthetic route is as follows.

Example 12: l-{l-[9-Methyl-8-(l-methyl-lH-pyrazol-4-yI)-9H-purin-6-yI]piperidin-4- yI}-l,3-dihydro-2H-benzimidazol-2-one (Compound 149)l H9-Methy -8-a-methyl-lH-pyrazol-^2H-benzimidazol-2-one[00207] To a solution of l-(l-(5-amino-6-(methylamino)pyrimidin-4-yl)piperidin-4-yl)- lH-benzo[d]imidazol-2(3H)-one (70 mg, 0.2 mmol) in anhydrous ethanol (8 mL) were added 1 -methyl- lH-pyrazole-4-carbaldehyde (34 mg, 0.3 mmol) and catalytic amount of hydrochloric acid (0.05 mL, 4M HCl in Dioxane, Aldrich). The reaction mixture was heated to 80 C for 18 hours. The resulting precipitate was collected by vacuum filtration, washed with ethanol (2 mL) and dried under reduced pressure, to give 62.6 mg (70% yield) of the title compound. NMR (400MHz, DMSO-d6): delta 10.84 (s, 1H), 8.41 (s, 1H), 8.25 (s, 1H), 8.02 (s, 1H), 7.13 (dd, 1H), 6.93 (m, 3H), 4.53 (m, 1H), 3.92 (s, 3H), 3.81 (d, 3H), 3.33 (m, 2H), 3.24 (m, 2H), 2.33 (m, 2H), 1.82 (d, 2H); MS (EI) for C22H23N9O: 430.4 (MH+).

The chemical industry reduces the impact on the environment during synthesis 1-Methyl-1H-pyrazole-4-carbaldehyde. I believe this compound will play a more active role in future production and life.

Reference:
Patent; EXELIXIS, INC.; PATRICK, Kearney; WO2012/37226; (2012); A1;,
Pyrazole – Wikipedia,
Pyrazoles – an overview | ScienceDirect Topics

Researchers who often do experiments know that organic synthesis is a process of preparing more complex target molecules from simple raw materials through one or more chemical reactions. Generally, it requires fewer steps, and cheap raw materials. 578008-32-9, name is tert-Butyl 3-amino-5-methyl-1H-pyrazole-1-carboxylate, A new synthetic method of this compound is introduced below., Recommanded Product: tert-Butyl 3-amino-5-methyl-1H-pyrazole-1-carboxylate

2-(2-Chloro-4-trifluoromethyl-phenyl)-4-(5-methyl-1H-pyrazol-3-ylamino)-2H-phthalazin-1-one: 4-Bromo-2-(2-chloro-4-trifluoromethyl-phenyl)-2H-phthalazin-1-one (obtained from the above phthalazine-1,4-dione by bromination with POBr3 in analogy to Method R, as reported above) (0.15 g, 0.37 mmol), 3-amino-5-methyl-pyrazole-1-carboxylic acid tert-butyl ester (0.080 g, 0.41 mmol), Cs2CO3 (0.033 g, 0.34 mmol), tris-(dibenzylideneacetone)-dipalladium (0.017 g, 0.01 9 mmol) and 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene (0.022 g, 0.037 mmol) in 2 ml dry dioxane under nitrogen were heated to 100 C. for 18 hours, and then allowed to cool to RT. H2O was added and the solvent was evaporated in vacuum. The resulting solid was collected by filtration. Purification of the raw product by preparative HPLC gave the title compound (0.069 g, 44% yield). 1H-NMR: (400 MHz, D6-DMSO) 11.92 (1H, s), 9.34 (1H, s), 8.54 (1H, d), 8.35 (1H, d), 8.14 (1H, s), 8.01 (1H, t), 7.92 (3H, m), 6.06 (1H, s), 2.14 (3H, s); MS (ESI+)=420.23 (M+H)+.

The basis of chemical reaction formula synthesis, the synthesis route is composed of some specific reactions and combined according to certain logical thinking. We look forward to the emergence of more reaction modes in the future.

Reference:
Patent; Roche Palo Alto LLC; US2007/219195; (2007); A1;,
Pyrazole – Wikipedia,
Pyrazoles – an overview | ScienceDirect Topics

Application of 4522-35-4, 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. 4522-35-4, name is 3-Iodo-1H-pyrazole belongs to pyrazoles-derivatives compound, it is a common compound, a new synthetic route is introduced below.

(1) a nitrogen gas atmosphere, in tetrahydrofuran (16 mL) solution of 3-iodo -1H- pyrazole (1.55 g), sodium hydride at 0 C. (purity 55%, 384 mg) and stirred for 15 minutes added.There was added dropwise a tetrahydrofuran solution (10 mL) of ethyl bromoacetate (1.06 mL), and stirred for 3 hours. Under ice-cooling, and extracted with chloroform by the addition of 1M hydrochloric acid to the reaction mixture. Organic layer was dried over anhydrous magnesium sulfate, and after filtration, the solvent was evaporated under reduced pressure. The obtained residue was purified by silica gel column chromatography (hexane: ethyl acetate = 100: 0 ? 70: 30) to give the (3-iodo -1H- pyrazol-1-yl) colorless oil Ethyl acetate (1.64 g) It was obtained as a material.

The synthetic route of 3-Iodo-1H-pyrazole has been constantly updated, and we look forward to future research findings.

Reference:
Patent; TAISHO PHARMACEUTICAL COMPANY LIMITED; NISSAN CHEMICAL INDUSTRIES LIMITED; KURODA, SHOICHI; USHIKI, YASUNOBU; KAWAGUCHI, TAKANORI; FUSEGI, KEIKO; BOHNO, MASAHIRO; IMAI, YUDAI; UNEUCHI, FUMITO; IWAKIRI, KANAKO; TANAKA, HIROAKI; BOHNO, AYAKO; CHONAN, TOMOMICHI; ITOH, SHIN; OTA, HIROFUMI; ISHIYAMA, SEISHI; OKADA, TAKUYA; SASAKO, SHIGETADA; MONMA, SOUICHI; NIWA, MARIE; OKADA, TAKUMI; (289 pag.)JP2015/231988; (2015); A;,
Pyrazole – Wikipedia,
Pyrazoles – an overview | ScienceDirect Topics

Researchers who often do experiments know that organic synthesis is a process of preparing more complex target molecules from simple raw materials through one or more chemical reactions. Generally, it requires fewer steps, and cheap raw materials. 288-13-1, name is 1H-Pyrazole, A new synthetic method of this compound is introduced below., Recommanded Product: 288-13-1

General procedure: In a 50 mL round-bottom flask, pyrrole or pyrazole or indole(2.0 mM), 4-iodonitrobenzene (4.4 mM, 1.2 equiv.), Pd(PPh3)4 (2.5mol%) and K2CO3(2.2 equiv.) were added under continuous stirring condition. To this, 5.0 mL of dry DMA was then added under reflux condition at 110 C for 20 h. After completion of the reaction (monitored by thin-layer chromatography), the reaction mixture was allowed to cool at room temperature and diluted with distilled water. After that the solution was extracted with ethyl acetate and the organic layer was dried over anhydrous MgSO4, which was subjected to column chromatography to obtain the corresponding products.

The synthetic route of 288-13-1 has been constantly updated, and we look forward to future research findings.

Reference:
Article; Nandi, Debkumar; Siwal, Samarjeet; Choudhary, Meenakshi; Mallick, Kaushik; Applied Catalysis A: General; vol. 523; (2016); p. 31 – 38;,
Pyrazole – Wikipedia,
Pyrazoles – an overview | ScienceDirect Topics

Adding a certain compound to certain chemical reactions, such as: 83-10-3, name is 1,5-Dimethyl-3-oxo-2-phenyl-2,3-dihydro-1H-pyrazole-4-carboxylic acid, belongs to pyrazoles-derivatives compound, can increase the reaction rate and produce products with better performance than those obtained under traditional synthetic methods. Here is a downstream synthesis route of the compound 83-10-3, Application In Synthesis of 1,5-Dimethyl-3-oxo-2-phenyl-2,3-dihydro-1H-pyrazole-4-carboxylic acid

(Step 11) N-(4-(5-bromopyrrolo[1,2-b]pyridazin-4-yloxy)-3-fluorophenyl)-1,5-dimethyl-3-oxo-2-phenyl-2,3-dihydro-1H-pyrazole-4-carboxamide; To a solution of 4-(5-bromopyrrolo[1,2-b]pyridazin-4-yloxy)-3-fluoroaniline (57 mg, 0.178 mmol) and 1,5-dimethyl-3-oxo-2-phenyl-2,3-dihydro-1H-pyrazole-4-carboxylic acid (124 mg, 0.534 mmol) prepared in Preparation Example 1 in dimethylformamide (2 mL), HATU (270 mg, 0.711 mmol) and triethylamine (0.1 mL, 0.711 mmol) were sequentially added and stirred at 50 C. overnight. The resulting reaction mixture was concentrated under reduced pressure and the resulting residue was extracted with dichloromethane and water. The organic layer was separated, dried with magnesium sulfate, and then filtered. The filtrate was concentrated under reduced pressure. The resulting residue was purified by silica gel chromatography (10% ethyl acetate in dichloromethane) to give the target compound as a white solid (60 mg, 0.111 mmol, 63% yield).MS (ESI pos. ion) m/z: 536, 538 (MH+). Calc’d exact mass for C25H19Br79FN5O3: 535, Calc’d exact mass for C25H19Br81FN5O3: 537.1H NMR (400 MHz, CDCl3): 10.89 (br s, 1H), 7.91 (dd, J=12.4 Hz, 2.4 Hz, 1H), 7.78 (d, J=5.6 Hz, 1H), 7.65 (d, J=2.8 Hz, 1H), 7.59-7.54 (m, 2H), 7.52-7.46 (m, 1H), 7.38-7.35 (m, 2H), 7.31-7.28 (m, 1H), 7.19 (t, J=8.8 Hz, 1H), 6.80 (d, J=2.8 Hz, 1H), 5.67 (dd, J=5.6 Hz, 1.2 Hz, 1H), 3.38 (s, 3H), 2.80 (s, 3H).

At the same time, in my other blogs, there are other synthetic methods of this type of compound, 1,5-Dimethyl-3-oxo-2-phenyl-2,3-dihydro-1H-pyrazole-4-carboxylic acid, and friends who are interested can also refer to it.

Reference:
Patent; NEOPHARM CO., LTD.; US2011/183983; (2011); A1;,
Pyrazole – Wikipedia,
Pyrazoles – an overview | ScienceDirect Topics

Reference of 368870-03-5, These common heterocyclic compound, 368870-03-5, name is (4-(1H-Pyrazol-1-yl)phenyl)methanamine, 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.

5 mmol of compound III was dissolved in 20 mL of N, N-dimethylacetamide (DMA),20 mmol of N, N-diisopropylethylamine (DIPEA) was then added.6 mmol of intermediate IIb was added thereto at room temperature. Gabi,The temperature was raised to 90 C for 22 hours.Stop the reaction, remove the solvent under reduced pressure,The obtained crude product was separated by column chromatography to obtain the target compound Ib.

The synthetic route of 368870-03-5 has been constantly updated, and we look forward to future research findings.

Reference:
Patent; Nantong University; Dai Hong; Liang Kai; Ni Yadan; Li Jinfeng; Shi Yujun; Gao Lei; Sui Ying; Zhou Huanyu; Zhou Qian; Yan Ruijian; (7 pag.)CN110713460; (2020); A;,
Pyrazole – Wikipedia,
Pyrazoles – an overview | ScienceDirect Topics

Some common heterocyclic compound, 34605-66-8, name is 3-(2,5-Dimethyl-1H-pyrrol-1-yl)-1-methyl-1H-pyrazole, molecular formula is C10H13N3, 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. Quality Control of 3-(2,5-Dimethyl-1H-pyrrol-1-yl)-1-methyl-1H-pyrazole

A stirred solution of 3-(2,5-dimethylpyrrol-1-yl)-1-methyl-pyrazole (2.000g, 11 .4lmmol) intetrahydrofuran (l5mL) was cooled to -78C under an atmosphere of nitrogen. Butyllithium (1.6mol in hexanes)(7.8mL, 12.SSmmol) was then added over l5mins. The resulting solution was stirred at -78C for 2 hours. 1-bromo-3-methyl-but-2-ene (1.701g, 11 .4lmmol) dissolved in THE (5mL) was then added over 1 Omins, maintaining a temperature below -60C. The reaction mixture was stirred cold for a further 10 minutes and then allowed to warm slowly to ambienttemperature over a period of 1 hour. Saturated aqueous ammonium chloride was added to quench the reaction. Ethyl acetate was then added and the layers separated. The aqueous layer was extracted three times with ethyl acetate. The combined organics washed with water, dried over Mg504 and concentrated in vacuo to brown oil. Chromatography on silica gel gave yellow oil 1.728g (62%). 1H NMR (CDCI3) 5.90 (s, 1H), 5.83 (s, 2H), 5.30-5.25 (m, 1H), 3.79 (s, 3H),3.36-3.32(m, 2H), 2.11 (s, 6H), 1.78(s, 3H), 1.73(s, 3H).

These compound has a wide range of applications. It is believed that with the continuous development of the source of the synthetic route 34605-66-8, its application will become more common.

Reference:
Patent; SYNGENTA PARTICIPATIONS AG; SYNGENTA LIMITED; BOEHMER, Jutta Elisabeth; PHADTE, Mangala; LONGSTAFF, Adrian; MORRIS, James Alan; DESSON, Timothy Robert; HOTSON, Matthew Brian; DOWLING, Alan John; WHITTINGHAM, William Guy; DALENCON, Anne Jacqueline; DE FRAINE, Paul John; THOMPSON, Alison Jane; HACHISU, Shuji; WO2015/18433; (2015); A1;,
Pyrazole – Wikipedia,
Pyrazoles – an overview | ScienceDirect Topics

Electric Literature of 37687-24-4, The chemical industry reduces the impact on the environment during synthesis 37687-24-4, name is Diethyl 3,5-pyrazoledicarboxylate, I believe this compound will play a more active role in future production and life.

A mixture of diethyl 1H-pyrazole-3,5-dicarboxylate (5.95 g, 28.0 mmol), 2-bromo-1-(2,3-dihydro-1H-inden-5-yl)ethan-1-one (Intermediate 129A, 9.57 g, 70% purity, 28.0 mmol) and potassium carbonate (9.68 g, 70.1 mmol) in acetone (250 ml) was stirred at RT overnight. Then, the mixture was filtered, and the filtrate was concentrated to afford the crude product which was used in the next step without further purification. Yield: 10.4 g (65% of theory, 65% purity). LC/MS [Method 7]: Rt = 1.15 min; MS (ESIpos): m/z = 371 [M+H]+.

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, Diethyl 3,5-pyrazoledicarboxylate, other downstream synthetic routes, hurry up and to see.

Reference:
Patent; BAYER AKTIENGESELLSCHAFT; BAYER PHARMA AKTIENGESELLSCHAFT; MUeLLER, Steffen; SCHOHE-LOOP, Rudolf; ORTEGA, HERNANDEZ, Nuria; SUeSSMEIER, Frank; JIMENEZ NUNEZ, Eloisa; BRUMBY, Thomas; LINDNER, Niels; GERDES, Christoph; POOK, Elisabeth; BUCHMUeLLER, Anja; GAUGAZ, Fabienne, Zdenka; LANG, Dieter; ZIMMERMANN, Stefanie; EHRMANN, Alexander, Helmut, Michael; GERISCH, Michael; LEHMANN, Lutz; TIMMERMANN, Andreas; SCHAeFER, Martina; SCHMIDT, Georg; SCHLEMMER, Karl-Heinz; FOLLMANN, Markus; KERSTEN, Elisabeth; WANG, Vivian; GAO, Xiang; WANG, Yafeng; (801 pag.)WO2019/219517; (2019); A1;,
Pyrazole – Wikipedia,
Pyrazoles – an overview | ScienceDirect Topics

These common heterocyclic compound, 82560-12-1, name is 3-Amino-5-tert-butylpyrazole, 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. name: 3-Amino-5-tert-butylpyrazole

3-Tert-butyl-1 H-pyrazol-5-amine (J-lll) (1 eq., 40 g) was dissolved in dilute HCI (120 ml of HCI in 120 ml of water) and mixed dropwise with NaNO2 (1.03 eq., 25 g in 100 ml) at 0 – 5 C over a period of 30 min. After stirring for 30 minutes, the reaction mixture was neutralised with Na2C03. A diazonium salt obtained by reaction of KCN (2.4 eq., 48 g), water (120 ml) and CuCN (1.12 eq., 31 g) was added dropwise to the reaction mixture within 30 min and the mixture was stirred for a further 30 min at 75 C. After complete reaction, the reaction mixture was extracted with EE (3 x 500 ml), the combined organic phases were dried over sodium sulphate and the solvent was removed under vacuum. The purification (Si02, 20 % EE/hexane) of the residue by column chromatography produced a white solid (J- IV) (6.5 g, 15.1 % yield).

The synthetic route of 3-Amino-5-tert-butylpyrazole has been constantly updated, and we look forward to future research findings.

Reference:
Patent; GRUeNENTHAL GMBH; FRANK, Robert; CHRISTOPH, Thomas; LESCH, Bernhard; LEE, Jeewoo; WO2012/62462; (2012); A1;,
Pyrazole – Wikipedia,
Pyrazoles – an overview | ScienceDirect Topics