Category: pyrazoles-derivatives

Electric Literature of 120068-79-3, 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. 120068-79-3, name is 5-Amino-1-(2,6-dichloro-4-(trifluoromethyl)phenyl)-1H-pyrazole-3-carbonitrile belongs to pyrazoles-derivatives compound, it is a common compound, a new synthetic route is introduced below.

Example 1; Sulfinylation of 5-amino-1-[2,6-dichloro-4-(trifluoromethyl)phenyl]-1 H- pyrazole-3-carbonitrile with triethylamine hydrochloride, sodium trifluoromethylsulfinate and thionylchloride, in 6.5 molar equivalents of tolueneWithin a 3-neck, 50 ml. round bottom flask equipped with a magnetic stirrer bar and a thermometer were placed vacuum dried sodium trifluoromethylsulfinate (4.29 g, 27.5 mmol), vacuum dried triethylamine hydrochloride (5.16 g, 37.5 mmol), and 13 ml. an- hydrous toluene (6.5 molar equivalents relative to 5-amino-1-[2,6-dichloro-4-(trifluoromethyl)phenyl]-1 H-pyrazole-3-carbonitrile) under an argon atmosphere. After cooling to 00C to 5 0C with an ice bath, thionylchloride (3.57 g, 30 mmol) was added slowly while keeping the reaction temperature below 5 0C. After stirring for another 30 min, vacuum dried 5-amino-1-(2,6-dichloro-4-trifluoromethyl-phenyl)-1 H-pyrazole-3- carbonitrile (8.03 g, 25 mmol, 99 % purity) was added at 5 0C, and the reaction mixture was heated to 50 0C within 5 min by a preheated water bath. The temperature of 50 0C was kept for another 6 hours before quenching the reaction with 50 ml. of saturated NaHCO3 solution. The resulting suspension was diluted with 30 ml. of ethylacetate. After phase separa- tion the organic layer was washed once with saturated NaHCtheta3 solution and concentrated under reduced pressure until dryness. The crude product was crystallized from refluxing toluene (100 g) affording the title compound as a white crystalline powder (8.06 g, 70 % yield, 94 % purity by quantitative HPLC). 1H-NMR (Bruker DRX-500, d6- DMSO): delta [ppm]: 8.33 (s), 7.57 (s).; Example 3; Sulfinylation of 5-amino-1 -[2,6-dichloro-4-(trifluoromethyl)phenyl]-1 H- pyrazole-3-carbonitrile via addition of a mixture of sodium trifluoromethylsulfinate, triethylamine hydrochloride and thionylchloride to 5-amino-1-[2,6-dichloro-4- (trifluoromethyl)phenyl]-1 H-pyrazole-3-carbonitrileWithin a 3-neck, 50 ml. round bottom flask equipped with a magnetic stirrer bar and a thermometer were placed vacuum dried sodium trifluoromethylsulfinate (4.29 g, 27.5 mmol), vacuum dried triethylamine hydrochloride (5.16 g, 37.5 mmol), and 10 g anhydrous toluene under an argon atmosphere. After cooling to 0 – 5 0C with an ice bath thionylchloride (3.57 g, 30 mmol) was added while keeping the reaction temperature below 5 0C. After stirring for another 30 min the cooled sulfinic acid solution was added at once to a stirred suspension of vacuum dried 5-amino-1-(2,6-dichloro-4- trifluoromethyl-phenyl)-1 H-pyrazole-3-carbonitrile (8.03 g, 25 mmol, 99 % purity) in 5 g toluene with a temperature of 50 0C. The temperature of 50 0C was kept for another 5 hours before quenching the reaction with 50 ml. of saturated NaHCU3 solution. The resulting suspension was diluted with 30 ml. of ethylacetate. After phase separation the organic layer was washed once with saturated NaHCU3 solution and concentrated under reduced pressure until dryness. The crude product was crystallized from refluxing toluene (100 g) affording the title compound as a white crystalline powder (7.25 g, 63 % yield, 94 % purity by quantitative HPLC). 1H-NMR (Bruker DRX-500, d6- DMSO): delta [ppm]: 8.33 (s), 7.57 (s).; Example 11; Sulfinylation of 5-amino-1 -[2,6-dichloro-4-(trifluoromethyl)phenyl]-1 H- pyrazole-3-carbonitrile with thionylchloride, triethylamine hydrochloride and dosage of potassium trifluoromethylsulfinateWithin a 750 mL reactor with a mechanical stirrer and a thermometer were placed vac- uum dried triethylamine hydrochloride (51.1 g, 368 mmol), 147 g anhydrous toluene(6.5 molar equivalents relative to 5-amino-1-[2,6-dichloro-4-(trifluoromethyl)phenyl]-1 H- pyrazole-3-carbonitrile), and thionylchloride (35.7 g, 294 mmol) under an argon atmosphere. After cooling to 00C to 5 0C with external cooling, vacuum dried potassium trifluoromethylsulfinate (50.4 g, 296 mmol) was added in three equal portions every 10 min while keeping the reaction temperature below 5 0C. After stirring for another 30 min, vacuum dried 5-amino-1-(2,6-dichloro-4-trifluoromethyl-phenyl)-1 H-pyrazole-3- carbonitrile (79.5 g, 245 mmol, 99 % purity) was added at 5 0C, and the reaction mixture was kept at 5 0C for 60 min and then heated to 35 0C within 45 min. The temperature of 35 0C was kept for another 10 hours before quenching the reaction with 200 g of sodium hydroxide solution (10 wt.%).The resulting suspension was diluted with 176 mL of ethylacetate. After phase separation the organic layer was washed once with sodium hydroxide solution (10 wt.%). After phase separation, the organic layer was analyzed by quantitative HPLC (79 % yield). The content of compound F was below 2.9 weight percent in the crude mixture (without solvent). The product was crystallized from a mixture of ethylacetate and toluene affording the title compound as a white crystalline powder (77.1 g, 75 % yield, 98 % purity by quantitative HPLC).; Example 15; Sulfinylation of 5-amino-1-[2,6…

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, 5-Amino-1-(2,6-dichloro-4-(trifluoromethyl)phenyl)-1H-pyrazole-3-carbonitrile, other downstream synthetic routes, hurry up and to see.

Reference:
Patent; BASF SE; WO2008/55877; (2008); A1;,
Pyrazole – Wikipedia,
Pyrazoles – an overview | ScienceDirect Topics

Electric Literature of 67-51-6, These common heterocyclic compound, 67-51-6, name is 3,5-Dimethyl-1H-pyrazole, 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.

In a 250 ml reaction vessel, 3,5-dimethyl-1 H-pyrazole x51 (0.5 g, 5 mmol), I2 (0.79 g, 30 mmol) and CAN (1.71 g, 3 mmol) are dissolved in 70 ml of CH3CN and stirred at room temperature for 16 h. The solvent is evaporated, the residue dissolved in AcOEt and washed with a 10 % aqueous solution of Na2S2U3 and brine. The aqueous phase is re- extracted with AcOEt and the combined organic phases are dried over Na2SO4, filtered and concentrated to dryness to afford 1.15 g (100 %) of crude 4-iodo-3,5-dimethyl-1 H- pyrazole x52, which is used in the next step without further purification.LC-MS (MH+): 223.

Statistics shows that 3,5-Dimethyl-1H-pyrazole is playing an increasingly important role. we look forward to future research findings about 67-51-6.

Reference:
Patent; UCB S.A.; WO2006/128692; (2006); A2;,
Pyrazole – Wikipedia,
Pyrazoles – an overview | ScienceDirect Topics

Electric Literature of 20154-03-4, In the chemical reaction process, reaction time, type of solvent, can easily affect the result of the reaction, thereby determining the yield and properties of the reaction product. An updated downstream synthesis route of 20154-03-4 as follows.

To a stirred solution of 10 g (73.5 mmol) 3-(trifluoromethyl)-1H-pyrazole (3) in DMSO (150 ml) were added 9.9 g of potassium tert.-butoxide portion wise. After stirring for 5 minutes drop wise addition of 12 ml of iodoethane followed by stirring overnight were conducted. Water was added afterwards and the pH value was adjusted to 3 by using 1N HCl. The mixture was diluted with MTBE and extracted two more times with MTBE. The combined organic phase was washed with Na2S2O3-solution, water and brine yielding 8 g (67 percent) of the ionic liquid 8.

According to the analysis of related databases, 20154-03-4, the application of this compound in the production field has become more and more popular.

Reference:
Patent; SOLVAY SA; Braun, Max Josef; Fischer, Reiner; EP2662359; (2013); A1;,
Pyrazole – Wikipedia,
Pyrazoles – an overview | ScienceDirect Topics

Related Products of 17635-44-8, These common heterocyclic compound, 17635-44-8, name is 3,4,5-Tribromopyrazole, 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.

To a solution of D183 (0.95 g, 8.3 mmol) in THF (50mL) was added 3,4,5-tribromo-1 H- pyrazole (2.8 g, 9.1 mmol), PPh3 (4.3 g, 16.6 mmol) and DEAD (3.6 g, 20.7mmol) at 0-5 C under N2. The reaction solution was stirred at rt for 16 hrs. The reaction solution was poured into water (50 mL) and extracted with EtOAc (100 ml_x2). The combined organic layer was washed with brine, dried over anhydrous Na2S04and concentrated in vacuo. The crude product was purified by gel silica column chromatography (PE:EtOAc from 50:1 to 10:1 ) to afford the title compound as yellow oilsolid (2.4g, yield 71.6 %). LC-MS 403.0 (M+H)+.

The synthetic route of 17635-44-8 has been constantly updated, and we look forward to future research findings.

Reference:
Patent; GLAXOSMITHKLINE INTELLECTUAL PROPERTY DEVELOPMENT LIMITED; DING, Xiao; HO, Ming-Hsun; REN, Feng; YU, Haihua; ZHAN, Yang; (290 pag.)WO2019/12093; (2019); A1;,
Pyrazole – Wikipedia,
Pyrazoles – an overview | ScienceDirect Topics

Application of 10250-64-3, These common heterocyclic compound, 10250-64-3, name is 1-Methyl-3-phenyl-1H-pyrazole-5-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.

General procedure: To a solution of 19 (1.2 eq) and HOBt(1.4 eq) in DMF (0.5 M) were added EDCI (1.3 eq) and a solution of 15a-j or 16a-j (1.0 eq) in DMF (0.25 M), Et3N (3.5 eq) at 0 C. The reaction mixture was stirred at room temperature for 24 hours, then diluted in AcOEt. The organic phase was washed with water twice, saturated aqueous NaHCO3 three times, and brine, then dried over Na2SO4,filtered, and concentrated. The residue was purified by flash column chromatography to give intermediates 17a-j and 18a-j.

The synthetic route of 10250-64-3 has been constantly updated, and we look forward to future research findings.

Reference:
Article; Nakagawa, Hidehiko; Seike, Suguru; Sugimoto, Masatoshi; Ieda, Naoya; Kawaguchi, Mitsuyasu; Suzuki, Takayoshi; Miyata, Naoki; Bioorganic and Medicinal Chemistry Letters; vol. 25; 23; (2015); p. 5619 – 5624;,
Pyrazole – Wikipedia,
Pyrazoles – an overview | ScienceDirect Topics

Related Products of 50877-42-4, 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. 50877-42-4, name is 1-Benzyl-4-iodo-1H-pyrazole belongs to pyrazoles-derivatives compound, it is a common compound, a new synthetic route is introduced below.

A mixture of 1-benzyl-4-iodo-1H-pyrazole (1.05 g, 3.70 mmol) , bis (pinacolato) diboron (1.00 g, 3.94 mmol) , potassium acetate (1.00 g, 9.88 mmol) and Pd (dppf) Cl2(130 mg, 0.18 mmol) in DMSO (20 mL) was stirred at 80 under N2for 7 h. The reaction mixture was cooled to rt and quenched with water (50 mL) . The resulting mixture was extracted with EtOAc (50 mL × 3) . The combined organic layers were washed with saturated aqueous NaCl (50 mL × 2) , dried over anhydrous Na2SO4and concentrated in vacuo. The residue was purified by silica gel column chromatography eluted with PE/EtOAc (v/v) 5/1 to give a light yellow oily product (200 mg, 19.0) .[1088]MS (ESI, pos. ion) m/z: 282.3 [M+1]+ and[1089]1H NMR (600 MHz, CDCl3) : delta (ppm) 7.84 (s, 1H) , 7.69 (s, 1H) , 7.34 (m, 3H) , 7.25 (m, 2H) , 5.32 (s, 2H) , 1.32 (s, 12H)

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, 1-Benzyl-4-iodo-1H-pyrazole, other downstream synthetic routes, hurry up and to see.

Reference:
Patent; SUNSHINE LAKE PHARMA CO., LTD.; LIU, Bing; ZHANG, Yingjun; CHENG, Changchung; HUANG, Jiuzhong; BAI, Shun; REN, Xingye; LI, Zhi; ZHOU, Youbai; (368 pag.)WO2016/615; (2016); A1;,
Pyrazole – Wikipedia,
Pyrazoles – an overview | ScienceDirect Topics

Application of 31037-02-2, 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. 31037-02-2, name is Ethyl 5-amino-1-methyl-1H-pyrazole-4-carboxylate, This compound has unique chemical properties. The synthetic route is as follows.

5-Amino-1-methyl-1H-pyrazole-4-carboxylic acid ethyl ester (5.0 g, 29.6 mmol) was added portionwise to a mixture of tert-butyl nitrite (4.57 g, 44.3 mmol) and copper (II) bromide (7.92 g, 35.5 mmol) in acetonitrile (20 mL). The mixture was heated to 60C for 2 h. The resulting mixture was poured into 6M HCl (200 mL) and extracted with dichloromethane (3 x 250 mL). The combined organics was dried on magnesium sulfate and concentrated in vacuo. The crude material was purified by column chromatography (SiO2, 0% to 50% ethyl acetate in hexanes) to afford 5-bromo-1-methyl-1H-pyrazole-4-carboxylic acid ethyl ester as an off-white solid (4.7 g, 68%). 1H NMR (CDCl3) : 7.93 (s, 1H), 4.32 (q, J = 7.2 Hz, 2H), 3.92 (s, 3H), 1.36 (t, J = 7.0 Hz, 3H).

The chemical industry reduces the impact on the environment during synthesis Ethyl 5-amino-1-methyl-1H-pyrazole-4-carboxylate. I believe this compound will play a more active role in future production and life.

Reference:
Patent; F. HOFFMANN-LA ROCHE AG; HOFFMANN-LA ROCHE INC.; BOLIN, David Robert; DE VICENTE FIDALGO, Javier; HERMANN, Johannes Cornelius; TIVITMAHAISOON, Parcharee; YI, Lin; ZAK, Mark; WO2013/189904; (2013); A1;,
Pyrazole – Wikipedia,
Pyrazoles – an overview | ScienceDirect Topics

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. 948570-75-0, name is 1-(2-Methoxyethyl)-4-nitro-1H-pyrazole, This compound has unique chemical properties. The synthetic route is as follows., Computed Properties of C6H9N3O3

To a solution of l-(2-methoxyethyl)-4- nitro-pyrazole (3.0 g, 17.53 mmol) in MeOH (50 ml) was added 10 % Pd/C (300 mg) under N2. The suspension was degassed and purged with H2 several times. The mixture was stirred under a H2 atmosphere at 25 C for 3 h. The reaction mixture was filtered. The filtrate was concentrated under reduced pressure to give the title compound as a red oil (Y = 97 %). NMR (400 MHz, chloroform-rf) d ppm 7.16 (s, 1H), 7.09 (s, 1H), 4.16 (t, J= 5 Hz, 2H), 3.69 (t, J= 5 Hz, 2H), 3.32 (s, 3H), 2.93 – 2.83 (hr. s, 2H).

According to the analysis of related databases, 948570-75-0, the application of this compound in the production field has become more and more popular.

Reference:
Patent; NODTHERA LIMITED; HARRISON, David; WATT, Alan Paul; BOCK, Mark G.; (334 pag.)WO2019/121691; (2019); A1;,
Pyrazole – Wikipedia,
Pyrazoles – an overview | ScienceDirect Topics

Reference of 118430-74-3, 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. 118430-74-3 name is 3-Cyclopropyl-1-methyl-1H-pyrazol-5-amine, 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.

Intermediate I12.2, (0.20 g), 3-cyclopropyl-1-methyl-1H-pyrazole-5-amine (0.14 g), potassium t-butoxide (0.10 ml of a 1M THF solution) and dioxane (2 ml) were transferred to a microwave vial and heated under microwave irradiation under the following conditions: max power 150 W, T 150 C., 15 min; after the first cycle 0.05 mL of base were added and two more cycles of irradiation performed under the same conditions. The reaction mixture was evaporated to dryness, and the oily residue was purified by preparative LC-MS affording example 208 (as TFA salt) (0.09 g). HPLC (Rt)=7.12 min (method P)

At the same time, in my other blogs, there are other synthetic methods of this type of compound, 3-Cyclopropyl-1-methyl-1H-pyrazol-5-amine, and friends who are interested can also refer to it.

Reference:
Patent; BOEHRINGER INGELHEIM INTERNATIONAL GMBH; US2010/261687; (2010); 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.

2,4-dichloropyrimidine 2 (13.30 g, 89.31 mmol) and 3-amino-5-cyclopropylpyrazole 1 (11.00 g, 89.31 mmol) were dissolved in tetrahydrofuran (TFA) (100 ml) followed by theaddition of deionized water (100 ml). The solution was then treated with potassium acetate (261.9 g, 2.5 mol). The resulting mixture was kept at 55C for 48 h. The mixture was filtered to remove excess potassium acetate. The organic layer was separated and dried using magnesium sulfate and concentrated before loading on an AnaLogix silica column. Intermediate 3 was separated as previously reported (34). ?H NMR (400 MHz, DMSO) oe 12.14 (s, 1H), 10.23 (s,1H), 1.84 (m, 1H), 0.88 (m, 2H), 0.64 (m, 2H). ?3C NMR (100 MHz, DMSO) oe 161.4, 160.7,160.0, 153.9, 148.6, 147.8, 146.8, 8.4, 8.2. MS calculated for C,0H,0N5 235.06, found 236.15 (M).

These compound has a wide range of applications. It is believed that with the continuous development of the source of the synthetic route 5-Cyclopropyl-1H-pyrazol-3-amine, its application will become more common.

Reference:
Patent; THE REGENTS OF THE UNIVERSITY OF CALIFORNIA; SHOKAT, Kevan, M.; MENDEZ, Aaron, S.; (131 pag.)WO2016/22839; (2016); A1;,
Pyrazole – Wikipedia,
Pyrazoles – an overview | ScienceDirect Topics