Tag: M.W:100-200

Application of 37622-90-5, A common heterocyclic compound, 37622-90-5, name is Ethyl 4-pyrazolecarboxylate, molecular formula is C6H8N2O2, 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.

Preparation 8; Preparation of HI-ftert-butoxycarbonylt°iperidin-^yll-IH-pyrazole-Phicarboxylic acid; A mixture of ethyl 1H-pyrazole-4-carboxylate (700 mg, 5 mmol) and NaH 60% (6 mmol) was stirred under nitrogen at 00C for 1 hour in dry DMF (15 mL). ferf-Butyl 4-[(methylsulfonyl)oxy]piperidine-1-carboxylate (1.53 gr, 5.5 mmol) dissolved in 4 mL of dry DMF was added and the resulting solution was hetaed at 100C overnight . Reaction mixture was quenched with water and extracted (x3) with ethyl acetate. Collected organic phases were dried over Na2SU4, filtered and evaporated to dryness. Residue was dissolved in MeOH (20 mL) and water (5 mL) and KOH (1.12 gr, 20 mmol) was added. The resulting solution was stirred at room temperature 24 hours, then solvents removed under reduced pressure. The residue was taken-up with AcOEt and KHSO4 5% solution. Acqueous phase was extracted with EtOAc several times. Collected organic phases were dried with Na2SU4, filtered and evaporated to dryness affording 600 mg of the title compound. 1 H-NMR (400 MHz), delta (ppm, DMSO-de): 1.42 (s, 9H) 1.73 – 1.87 (m, 2H) 1.96 – 2.03 (m, 2H) 2.82 – 2.99 (m, 2H) 4.04 (d, J=12.93 Hz, 2H) 4.34 – 4.47 (m, 1H) 7.81 (s, 1H) 8.29 (s, 1H) 12.26 (br. s., 1H)

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; NERVIANO MEDICAL SCIENCES S.r.l.; MENICHINCHERI, Maria; BERTRAND, Jay, Aaron; MARCHIONNI, Chiara; NESI, Marcella; ORSINI, Paolo; PANZERI, Achille; WO2010/69966; (2010); A1;,
Pyrazole – Wikipedia,
Pyrazoles – an overview | ScienceDirect Topics

Reference of 26308-42-9,Some common heterocyclic compound, 26308-42-9, name is 3-Ethyl-1-methyl-1H-pyrazole-5-carboxylic acid, molecular formula is C7H10N2O2, 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 50 mL round bottom flask equipped with a magnetic stirrer was added 1-methyl-3-ethyl-1-hydrogen-pyrazole-5-carboxylic acid(154 mg, 1.0 mmol, 1.0 eq),Selectfluor (708 mg, 2.0 mmol, 2.0 eq), lithium acetate (264 mg, 4.0 mmol,4.0 eq); then dichloroethane (3.3 mL) and water (1.7 mL) were added as solvent; the reaction vessel was sealed at 50 C in an oil bathAnd the mixture was heated and stirred for 15 hours. After the reaction was completed, the reaction mixture was extracted twice with 20 mL of ether, and the organic phaseAnd washed with saturated brine, and then dried over anhydrous sodium sulfate. After drying, the organic solvent was dried under reduced pressure to obtain crude productThe crude product was subjected to column separation using analytically pure n-pentane as eluent to give the final product: 1,1′-diethyl-5,5′-difluoro-3,3′-dimethyl-1-hydrogen, 1′-hydro-4,4′-bipyrazole as a colorless oil in 82% yield.

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

Reference:
Patent; Central South University; Tang, Zhenyu; Yuan, Xi; Yao, Jianfei; (24 pag.)CN106397377; (2017); A;,
Pyrazole – Wikipedia,
Pyrazoles – an overview | ScienceDirect Topics

Adding a certain compound to certain chemical reactions, such as: 5334-39-4, name is 3-Methyl-4-nitro-1H-pyrazole, 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 5334-39-4, name: 3-Methyl-4-nitro-1H-pyrazole

Intermediate 6B 1-(4-methoxybenzyl)-3-methyl-4-nitro-1 H-pyrazole and 1-(4-methoxybenzyl)-5- methyl-4-nitro- 1 H-pyrazole In analogy to intermediate 4B), 2.5 g (19.7 mmol) 3-methyl-4-nitro-1 H-pyrazole and 3.70 g (23.6 mmol) 1 -(bromomethyl)-4-methoxybenzene were reacted to give after purification of the crude product via a Biotage chromatography system (50g snap KP- Si L column, hexane / 10 – 100% ethyl acetate, then ethyl acetate / 0 – 25% methanol) 4.9 g (100%) of the desired title compounds as a mixture. 1H-NMR (300 MHz, DMSO d6) delta (ppm) = 2.38 / 2.60 (s, 3H), 3.72 / 3.72 (s, 3H), 5.21 / 5.34 (s, 2H), 6.85 – 6.94 (m, 2H), 7.18 / 7.29 (d, 2H), 8.24 / 8.89 (s, 1 H). Intermediate 6C 1-(4-methoxybenzyl)-3-methyl-1 H-pyrazol-4-amine and 1-(4-methoxybenzyl)-5- methyl- 1 H-pyrazol-4-amine 4.94 g (20.0 mmol) 1 -(4-methoxybenzyl)-3-methyl-4-nitro-1 H-pyrazole and 1 -(4- methoxybenzyl)-5-methyl-4-nitro-1 H-pyrazole (intermediate 6B) was dissolved in 78 mL methanol, and 522 mg palladium on carbon (10 wt. %) and 10.1 g (160 mmol) ammonium formiate were added. The reaction mixture was heated for 1 h at 80 C. Afterwards the suspension was filtered through Celite and the filtrate was evaporated. The residue was diluted with 50 mL water and this phase was extracted three times with ethyl acetate. The combined organic phase was washed with brine, dried over sodium sulfate, filtered and evaporated to obtain a crude material which was purified via a Biotage chromatography system (100g snap KP-Sil column, hexane / 20 – 70% ethyl acetate) to give 3.64 g (84%) of the desired title compounds as a mixture. 1H-NMR (400 MHz, DMSO d6) delta (ppm) = 1.96 / 1.98 (s, 3H), 3.55 (s, 2H), 3.70 / 3.71 (s, 3H), 4.94 / 5.05 (s, 2H), 6.83 – 6.88 (m, 2H), 6.90 / 6.94 (s, 1 H), 6.98 – 7.02 / 7.09 – 7.14 (m, 2H).

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, 3-Methyl-4-nitro-1H-pyrazole, other downstream synthetic routes, hurry up and to see.

Reference:
Patent; BAYER PHARMA AKTIENGESELLSCHAFT; BUCHMANN, Bernd; HEISLER, Iring; MUeLLER, Thomas; CLEVE, Arwed; HEROULT, Melanie; NEUHAUS, Roland; PETRUL, Heike; QUANZ-SCHOeFFEL, Maria; (248 pag.)WO2016/12481; (2016); A1;,
Pyrazole – Wikipedia,
Pyrazoles – an overview | ScienceDirect Topics

Application of 34334-96-8,Some common heterocyclic compound, 34334-96-8, name is 3-Methyl-5-nitro-1H-pyrazole, molecular formula is C4H5N3O2, 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: Mcthancsulfonyl chloride (6.683 mL, 1.48 g/mL, 86.338 mmol) was added to a solution of 3-methoxy-3-methylbutanol (5 g, 42.31 mmol ) and Et-,N (17.661 mL, 0.728 g/mL, 127.059 mmol ) in DCM (477.33 mL, 1 .326 g/mL, 7452.28 mmol) at rt and the reaction mixture was stirred for 18h. Water was added. The organic layer was separated, washed with I N HCI(aq) then with brine before drying over MgSC>4. The organic layer was filtered and evaporated to afford a mixture on intermediate 778 and 778′ (10.3 g, quantitative yield ) that was used directly in the next step. Bromo-3-methoxypropane (1.20 mL, 10.51 mmol) was added at rt to a mixture of 5-nitro-lH-pyrazole (1.00 g, 8.84 mmol), 2 (2.35 g, 17.00 mmol) in DMF (10 mL).This reaction was stirred in a sealed tube at 120 C using one single mode microwave(Biotage Initiator EXP 60) with a power output ranging from 0 to 400 W for 30 min.Then, water was added and this mixture was extracted twice with EtOAc. The organic10 layers were mixed, dried over MgS04, filtered and the solvent was evaporated untildryness. The residue was purified by column chromatography on silica gel (IrregularSiOH, 40 |im, 80 g, mobile phase: gradient from 70% heptane, 29% EtOAc, 1% MeOH(+10% NH4OH) to 40% heptane, 52% EtOAc, 8% MeOH (+10% NH4OH)). The purefractions were collected and the solvent was evaporated until dryness to give 1.39 g of15 intermediate 56 (85% yield) and 267 mg of intermediate 56? (16% yield). Theseintermediates were used as it in the next step.

The synthetic route of 34334-96-8 has been constantly updated, and we look forward to future research findings.

Reference:
Patent; JANSSEN PHARMACEUTICA NV; STANSFIELD, Ian; QUEROLLE, Olivier, Alexis, Georges; LIGNY, Yannick, Aime, Eddy; GROSS, Gerhard, Max; JACOBY, Edgar; MEERPOEL, Lieven; GREEN, Simon, Richard; HYND, George; KULAGOWSKI, Janusz, Jozef; MACLEOD, Calum; MANN, Samuel, Edward; (472 pag.)WO2018/2217; (2018); A1;,
Pyrazole – Wikipedia,
Pyrazoles – an overview | ScienceDirect Topics

Application of 146941-72-2, 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. 146941-72-2, name is 4-Bromo-1-methyl-1H-pyrazol-3-amine, This compound has unique chemical properties. The synthetic route is as follows.

General procedure: A soln. of amine BB-34 (1 eq) and aldehyde or ketone BB-12 (1.05 to 1.1 eq) in MeOH (2 to 4 mL/mmol) was stirred for 1 h at RT. NaBI-U (1.6 to 2 eq) was added portionwise at 0C and the rxn mixture was stirred at a given temperature for a given time (see Table 52). It was quenched with H2O at 0C and extracted with EtOAc. The combined org. phases were washed with brine, dried over MgSCh and concentrated in vacuo. When necessary, the crude was purified by CC using EtOAc/MeOH

The chemical industry reduces the impact on the environment during synthesis 4-Bromo-1-methyl-1H-pyrazol-3-amine. I believe this compound will play a more active role in future production and life.

Reference:
Patent; IDORSIA PHARMACEUTICALS LTD; FROIDEVAUX, Sylvie; HUBLER, Francis; MURPHY, Mark; RENNEBERG, Dorte; STAMM, Simon; (266 pag.)WO2019/137927; (2019); 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. 14521-80-3, name is 3-Bromo-1H-pyrazole, A new synthetic method of this compound is introduced below., Safety of 3-Bromo-1H-pyrazole

Example 9. Synthesis of 4-(3-(3-oxa-9-azaspiro[5.5]undecan-9-yl)-lH-pyrazol-l- yl)-2-(2,6-difluorophenyl)-6,7-dihydro-5H-pyrrolo [3,4-b] pyridin-5-one, 1-9 Synthesis of compound 9.2. To a mixture of 1.4 (0.4g, 1.05mmol, l .Oeq) in 1 ,4- dioxane (5.0 ml) was added 3-Bromo-lH-pyrazole (0.169g, 1.15mmol, 1.1 eq) and K2CO3 (0.29g, 2.10mmol, 2.5eq). The reaction mixture was degassed for 10 min. under argon atmosphere, then Pd2(dba)3 (0.096 g, 0.01 mmol, O. leq) and Xantphos (0.121g, 0.2mmol, 0.2eq) were added, and again degassed for 5 min. The reaction was then heated at 100 C for 2 h. Upon completion of the reaction, reaction mixture was poured into water and product was extracted with EtOAc. Organic layers were combined, washed with brine solution, dried over Na2S04 and concentrated under reduced pressure to obtain crude which was purified by column chromatography to provide 9.2 (0.1 1 g, 21.4%). MS(ES): m/z 9 [M+H]+.

The synthetic route of 14521-80-3 has been constantly updated, and we look forward to future research findings.

Reference:
Patent; NIMBUS LAKSHMI, INC.; MASSE, Craig E.; GREENWOOD, Jeremy Robert; ROMERO, Donna L.; HARRIMAN, Geraldine C.; WESTER, Ronald T.; SHELLEY, Mee; KENNEDY-SMITH, Joshua Jahmil; DAHLGREN, Markus; MONDAL, Sayan; (342 pag.)WO2017/40757; (2017); 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. 5744-80-9, name is 3-Bromo-1,5-dimethyl-1H-pyrazole, A new synthetic method of this compound is introduced below., Formula: C5H7BrN2

General procedure: A mixture of 19d (0.20 g, 0.81 mmol), bis(pinacolato)-diboron(0.44 g, 1.72 mmol), Pd(Ph3P)4 (0.050 g, 0.043 mmol), and KOAc (0.17 g, 1.72 mmol) in 1,4-dioxane/H2O (30 mL, v/v, 5/1) was stirred at 100 C for 4 h under argon. It was cooled to room temperature. 10a(0.20 g, 0.54 mmol), Pd(Ph3P)4 (0.030 g, 0.029 mmol), and K2CO3(0.16 g, 1.14 mmol) were added to the reaction mixture at room temperature,and the mixture was stirred at 100 C for 12 h under argon. It was cooled to room temperature, and H2O was added to the mixture.The mixture was extracted with EtOAc. The organic layer was washed with brine, dried over anhydrous sodium sulfate, and the solvent was evaporated under reduced pressure. The residue was purified by silicagel column chromatography (eluting with 0-10% MeOH in DCM) to afford 10c as a pale yellow solid (0.13 g, 52%). 1H NMR (300 MHz,DMSO-d6) delta 8.27 (s, 1H), 7.78-7.75 (m, 1H), 7.54 (s, 1H), 7.18-7.15(m, 1H), 6.88-6.87 (m, 1H), 6.15 (s, 1H), 6.02-5.93 (m, 1H), 5.82-5.76(m, 1H), 5.32-5.27 (m, 1H), 5.03 (s, 2H), 3.93 (s, 3H), 3.64 (m, 4H),3.33 (m, 4H); 13C NMR (75 MHz, DMSO-d6) delta 161.85, 158.29, 156.01,153.75, 152.72, 142.91, 140.24, 139.17, 138.42, 137.18, 131.81,128.07, 126.97, 126.44, 124.53, 119.49, 116.23, 97.23, 65.97, 60.28,51.65, 41.76; MS (ESI) m/z:460.3 [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:
Article; Yin, Yuan; Chen, Cheng-Juan; Yu, Ru-Nan; Shu, Lei; Zhang, Tian-Tai; Zhang, Da-Yong; Bioorganic and Medicinal Chemistry; vol. 27; 8; (2019); p. 1562 – 1576;,
Pyrazole – Wikipedia,
Pyrazoles – an overview | ScienceDirect Topics

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 118430-73-2 as follows. Formula: C8H15N3

Example I; Synthesis Example I (Preparation of Exemplified compound (1)); [Show Image] A mixture of 41.4 g of 4-nitroaniline (0.3 mol), 84 ml of conc. hydrochloric acid, 60 ml of acetic acid and 84 ml of propionic acid was stirred at an inner temperature ranging from 0 C to 5C. To the mixture was dropped 20.7 g (0.3 mol) of sodium nitrite per 45 ml of water at an inner temperature of 5 C or less. Thereafter, stirring was continued for 30 minutes at an inner temperature ranging from 0 C to 5 C. The resultant diazonium salt solution was dropped to 600 ml of acetonitrile solution containing 46.0 g (0.3 mol) of 5-tert-butyl-2-methyl-2H-pyrazole-3-ylamine at an inner temperature of 10 C or less. After the dropwise addition of the diazonium salt solution, the resultant reaction solution was kept stirring for 2 hours, followed by injection of 1000 ml of water. Then, the precipitated azo dye was separated by a filtration. Recrystallization of the produced crystals was performed with 1650 ml of methanol, to obtain Exemplified compound (1). Yield: 72 g (80%), Melting point: 199 C to 201 C. lambdamax (ethyl acetate solution) of Exemplified compound (1) was 444 nm.

According to the analysis of related databases, 118430-73-2, the application of this compound in the production field has become more and more popular.

Reference:
Patent; FUJIFILM Corporation; EP1903078; (2008); A2;,
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. 309740-49-6, name is Methyl 1-methyl-4-nitro-1H-pyrazole-5-carboxylate, A new synthetic method of this compound is introduced below., Recommanded Product: Methyl 1-methyl-4-nitro-1H-pyrazole-5-carboxylate

General procedure: To a solution of intermediate 488 (2.26 g, 9.45 mmol) in dry DCM (25.4 mL) was added dropwise diisobutylaluminium hydride (3.62 mL, 20.31 mmol) at – 50 C. The reaction mixture was stirred at – 50 C for 3 h then at rt for 2 h. The mixture was acidified at 0 C with a 3N aqueous solution of HCl and diluted with Et20. The organic layer was separated, washed with a IN aqueous solution of HCl, then twice with brine, dried over MgS04 and evaporated in vacuo. The residue (2.17 g) was purified by column chromatography on silica gel (irregular SiOH, 40 muiotaeta, 40 g, mobile phase: heptane/EtOAc, gradient from 100:0 to 60:40). The pure fractions were combined and the solvent was evaporated to give 536 mg of intermediate 489 (27% yield).

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; JANSSEN PHARMACEUTICA NV; STANSFIELD, Ian; QUEROLLE, Olivier, Alexis, Georges; LIGNY, Yannick, Aime, Eddy; GROSS, Gerhard, Max; JACOBY, Edgar; MEERPOEL, Lieven; GREEN, Simon, Richard; HYND, George; KULAGOWSKI, Janusz, Jozef; MACLEOD, Calum; MANN, Samuel, Edward; (472 pag.)WO2018/2217; (2018); A1;,
Pyrazole – Wikipedia,
Pyrazoles – an overview | ScienceDirect Topics

Related Products of 151049-87-5, These common heterocyclic compound, 151049-87-5, name is 3-Bromo-1-methyl-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.

To a solution of (5-(methoxycarbonyl)thiophen-3-yl)boronic acid (5.30 g, 28.5 mmol) and 3-bromo-i-methyl-iH-pyrazole (4.59 g, 28.5 mmol) in dioxane (108 mL) were added Pd(PPh3)4 (1.04 g, 1.42 mmol) and 1.5 M aqueous K3PO4solution (57 mL, 85 mmol). The resulting mixture was heated at 80 C for ih, then cooled, diluted with CH2C12, dried over Na2504, filtered through a pad of silic, and concentrated. The residue was purified by column chromatography on silica gel, eluting with EtOAc/hexanes, to give the title compound. MS: m/z = 223 (M + 1). ?H NMR (400 MHz, CDC13) oe 8.18 (s, iH), 7.80(s, iH), 7.40(s, iH), 6.44(s, iH), 3.96(s, 3H), 3.94 (s, 3H).

Statistics shows that 3-Bromo-1-methyl-1H-pyrazole is playing an increasingly important role. we look forward to future research findings about 151049-87-5.

Reference:
Patent; MERCK SHARP & DOHME CORP.; STUMP, Craig A.; CHEN, Yi Heng; LIU, Ping; MENG, Dongfang; WU, Jane; LI, Chun Sing; QI, Zhiqi; (163 pag.)WO2016/161572; (2016); A1;,
Pyrazole – Wikipedia,
Pyrazoles – an overview | ScienceDirect Topics