Month: November 2020

These common heterocyclic compound, 79463-77-7, name is Diphenyl N-cyanocarbonimidate, 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. 79463-77-7

To a stirred suspension of rac-allyl [3-(3,4-dichlorophenyl)-4,5-dihydro-lH-pyrazol-4-yl]carbamate (intermediate 7), 50.0 g (0.159 mol) in 2-propanol (860 mL) was added diphenyl N- cyanocarbonimidate, 38.0 g (0.159 mol). The reaction mixture was heated to reflux at which point the suspension dissolved into solution after a further 10 minutes at reflux a white precipitate formed. The reaction mixture was stirred at reflux for a further 1 hour before allowing to slowly cool to room temperature overnight. The precipitate was filtered, washing with diethyl ether (2 x 250 mL) and the resulting white solid was allowed to dry to yield rac-phenyl 4-{ [(allyloxy)carbonyl]amino}-N-cyano- 3-(3,4-dichlorophenyl)-4,5-dihydro-lH-pyrazole-l-carboximidate as a white solid, 48.6 g (67 %). NMR (400 MHz, DMSO-d6): delta [ppm] = 4.13 (apparent d, IH), 4.47 (m, 3H), 5.14 (dd, 2H), 5.51- 5.63 (m, IH), 5.79-5.90 (m, IH), 7.23 (d, 2H), 7.30 (t, IH), 7.45 (t, 2H), 7.79 (br m, 2H), 7.97 (br s, IH), 8.19 (d, IH). LCMS (method 3): Rt 1.75 min MS (ESI): [M + H]+ = 458.0

Chemical properties determine the actual use. Each compound has specific chemical properties and uses. We look forward to more synthetic routes in the future to expand reaction routes of 79463-77-7.

Reference:
Patent; BAYER PHARMA AKTIENGESELLSCHAFT; MOWAT, Jeffrey Stuart; STELLFELD, Timo; STRESEMANN, Carlo; HILLIG, Roman; KOeHR, Silke; STOeCKIGT, Detlef; WEISKE, Joerg; BRUMBY, Thomas; BARACK, Naomi; CHRIST, Clara; TER LAAK, Antonius; BADOCK, Volker; CRAMPTON, Rosemary Helen; STEFANUTI, Ian; (186 pag.)WO2016/91845; (2016); A1;,
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16588-02-6, Adding some certain compound to certain chemical reactions, such as: 16588-02-6, name is 2-Chloro-5-nitrobenzonitrile, 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 16588-02-6.

STARTING MATERIAL SYNTHETIC EXAMPLE 4 5-amino-2-piperidinobenzonitrile 2-Chloro-5-nitrobenzonitrile (20 g) and piperidine (9.34 g) were added to acetonitrile (100 ml) and the mixture was stirred at the refluxing temperature for 1 hr. The solvent was evaporated under reduced pressure. Diisopropyl ether was added to the residue to allow crystallization and the crystals were recrystallized from methanol to give 5-nitro-2-piperidinobenzonitrile (17 g).

Chemical properties determine the actual use. Each compound has specific chemical properties and uses. We look forward to more synthetic routes in the future to expand reaction routes of 16588-02-6.

Reference:
Patent; Ushio, Hiroyuki; Naito, Youichiro; Sugiyama, Naoki; Kawaguchi, Takafumi; Ohtsuki, Makio; Chiba, Kenji; US2003/203909; (2003); A1;,
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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 6393-40-4 as follows. 6393-40-4

A sample of 2 (6.13 mmol) was suspended in 55 mL ofdry methanol and the suspension was saturated with HCl(g) for 30 min. After 4 days stirring at room temperature, thesuspension was filtrated and the solid was washed with120 mL of ethyl ether. The yellow solid obtained wasdissolved in dry methanol and to this solution was added1 mL of isopropylamine; the mixture was heated underreflux for 3 h. The solvent was removed and the solidresulting was washed with 150 mL of ethyl ether and120 mL of ethyl acetate. 4-Amino-3-nitro-N-isopropylbenzamidine hydrochloride (5) This product was obtained as a yellow solid (63% yield);mp 259.5-261.6 C; IR (ATR) nu / cm-1 3456, 3161 (NH2),3047, 2942 (NH.HCl amidine), 1685 (C=N); 1H NMR(200 MHz, DMSO-d6) delta 8.44 (br s, 1H, H arom.), 8.08(br s, 2H, NH2), 7.76 (br s, 1H, H arom.), 7.20 (br s, 1H,H arom.), 4.07 (m, 1H, CH), 1.23 (d, J 5.6 Hz, 6H, CH3);13C NMR (50 MHz, DMSO-d6) delta 159.5, 148.6, 134.2,129.3, 127.2, 119.2, 115.5, 44.9, 21.5.

According to the analysis of related databases, 6393-40-4, the application of this compound in the production field has become more and more popular.

Reference:
Article; de Souza, Thiago B.; Oliver, Josidel C.; Gomes, Ana Paula B.; Aragao, Cicero Flavio S.; Ferreira, Leandro S.; Nogueira, Fernando Henrique A.; Dias, Amanda Latercia T.; Alves, Ricardo J.; Journal of the Brazilian Chemical Society; vol. 29; 6; (2018); p. 1304 – 1317;,
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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. 1527-89-5, name is 3-Methoxybenzonitrile belongs to nitriles-buliding-blocks compound, it is a common compound, a new synthetic route is introduced below. 1527-89-5

General procedure: In a pressurized sealed vial, aqueous hydroxylamine 50% w/w (4equiv) was added to a stirred solution of the appropriate carbonitrile(1 equiv) in absolute ethanol. The resulting mixture washeated at 90 C for 1 h. The solvent was then evaporated to drynessproviding the desired amidoxime quantitatively, which was usedwithout further purification.

The synthetic route of 1527-89-5 has been constantly updated, and we look forward to future research findings.

Reference:
Article; Quadri, Marta; Silnovi?, Almin; Matera, Carlo; Horenstein, Nicole A.; Stokes, Clare; De Amici, Marco; Papke, Roger L.; Dallanoce, Clelia; European Journal of Medicinal Chemistry; vol. 160; (2018); p. 207 – 228;,
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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 328-87-0 as follows. 328-87-0

Step A: Preparation of 2-(p-methoxybenzylthio)-5-trifluoromethylbenzoic acid A solution of p-methoxybenzylmercaptan (20.0 g, 0.13 mol) and sodium methoxide (7.0 g) in N,N-dimethylformamide (55 ml) was added dropwise with stirring under a nitrogen atmosphere to a solution of 4-chloro-3-cyanobenzotrifluoride (26.7 g, 0.13 mol) in N,N-dimethylformamide (35 ml) cooled in an ice bath. After stirring for 2 hours at room temperature, the reaction mixture was poured into ice-water and extracted several times with dichloromethane. The combined organic extracts were dried (sodium sulfate) and evaporated to afford in essentially quantitative yield, 2-(4′-methoxybenzylthio)-5-trifluoromethylbenzonitrile as an oil; 60 MHZ NMR spectrum in chloroform-d was in accord with the desired structure.

According to the analysis of related databases, 328-87-0, the application of this compound in the production field has become more and more popular.

Reference:
Patent; Merck & Co., Inc.; US4663344; (1987); A;,
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Adding some certain compound to certain chemical reactions, such as: 179898-34-1, name is 3-Bromo-5-fluorobenzonitrile, 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 179898-34-1. 179898-34-1

Example 15 1,1-Dimethylethyl[(3-bromo-5-fluorophenyl)methyl]carbamate NaBH4 (1.99 g, 52.5 mmol) was cautiously added to a solution of NiCl2 (1.36 g, 10.5 mmol), Boc2O (4.58 g, 21.0 mmol) and 3-bromo-5-fluorobenzonitrile (2.10 g, 10.5 mmol) in absolute ethanol (30 mL) at 0 C. (vigorous reaction with the formation of a black precipitate). Once the reaction had subsided the mixture was left to stir at room temperature for 30 min. Ethanol was removed under reduced pressure and the precipitate was dissolved in EtOAc, filtered and repeatedly washed with EtOAc. The combined organic phases were washed with saturated NaHCO3, and dried (Na2SO4). After removing the solvent, the product, was purified by flash column chomatography to yield 1,1-dimethylethyl[(3-bromo-5-fluorophenyl)methyl]carbamate (2.20 g, 69%). 1H NMR (400 MHz, CDCl3) delta 1.46 (S, 9H), 4.28-4.32 (m, 2H), 4.87 (br, 1H), 6.93-7.29 (m, 3H); 13C NMR (100 MHz, CDCl3) delta 20.3, 43.6, 44.1, 79.7, 80.0, 113.0, 114.0, 117.7, 122.5, 126.0, 123.0, 141.7, 155.9, 161.5, 164.0.

Chemical properties determine the actual use. Each compound has specific chemical properties and uses. We look forward to more synthetic routes in the future to expand reaction routes of 3-Bromo-5-fluorobenzonitrile.

Reference:
Patent; Glaxo Group Limited; US2009/203677; (2009); A1;,
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21667-62-9, 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. 21667-62-9 name is 3-(3-Chlorophenyl)-3-oxopropanenitrile, 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.

General procedure: To a stirred solution of carboxylic acid (1.0 eq.) in ethanol (2 M) was added thionyl chloride (2.0 eq.) dropwise at room temperature, and then refluxed for 2 hours. After it was cooled to room temperature, the reaction mixture was concentrated under reduced pressure to give crude product, which was chromatographed on silica gel column using 1:30 (v/v) EtOAc-petroleum ether solution as eluent to afford isolated product esters in 80% – 95% yields. Esters (1.0 eq.) were added dropwise to a stirred solution of acetonitrile (2.0 eq.) and NaH (3.0 eq.) in THF (2 M) at room temperature, and then refluxed for 1h . After it was cooled to room temperature, Water was added dropwise to the reaction mixture under ice bath until no gas bubbles generated, and employing dilute hydrochloric acid neutralization to neutral, extracted with ethyl acetate, dried over magnesium sulfate and concentrated in vacuo to give crude product which was chromatographed on silica gel column using 1:4 to 1:2 (v/v) EtOAc-petroleum ether solution as eluent to afford isolated product beta-ketonitriles, white or light yellow solid compounds in 50% – 85% yields. Finally, stirred in concentrated sulfuric acid (3 M) at room temperature for 5 to 10 hours. The reaction mixture was neutralized to neutral by ammonia water, extracted with ethyl acetate, dried over magnesium sulfate and concentrated in vacuo to give crude product which was chromatographed on silica gel column using 1:1 to 2:1 (v/v) EtOAc-petroleum ether solution as eluent to afford isolated product beta-ketoamides 1a-p, white solid compounds in 45% – 85% yields.

At the same time, in my other blogs, there are other synthetic methods of this type of compound, 3-(3-Chlorophenyl)-3-oxopropanenitrile, and friends who are interested can also refer to it.

Reference:
Article; Zheng, Congke; Zhang, Xiaohui; Ijaz Hussain, Muhammad; Huang, Mingming; Liu, Qing; Xiong, Yan; Zhu, Xiangming; Tetrahedron Letters; vol. 58; 6; (2017); p. 574 – 577;,
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Adding a certain compound to certain chemical reactions, such as: 21524-39-0, name is 2,3-Difluorobenzonitrile, belongs to nitriles-buliding-blocks 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 21524-39-0, 21524-39-0

Example 11; Step llA : Compound 11b; To a flame-dried flask, 2,3-difluorobenzonitirle (10 g, 72 mmol) was added along with dry ether (18 mL) and the mixture was allowed to stir at room temperature under nitrogen atmosphere. To the reaction flask, isopropyl Grignard reagent (72 mL, 2M in ether) was added slowly. The reaction mixture was then allowed to reflux (-40 C) for 2 hours. The reaction was then cooled to 0 C and was quenched with a mixture of water (30 mL) and 2N HC1 (60 mL). The biphasic reaction mixture stirred at 50 C for 3 hours then cooled to room temperature. The organic layer was separated and the aqueous phase was extracted with ether (2 x 75 mL). The organic phases were combined and were washed with saturated NaHC03 solution (2 x 100 mL) followed by washing with saturated NaCl solution (100 mL). The organic layer was isolated, dried over anhydrous MgS04, filtered, and evaporated to dryness in vacuo. Difluorophenyl ketone Ila, was recovered in 86% yield (11.6 g, 63 mmol) after purification by column chromatography on silica using 30% hexanes/dichloromethane as the eluent (Rf= 0. 8). Compound lla (11. 6 g, 63 mmol) was dissolved in 1,4-dioxane (63 mL) along with potassium carbonate (17. 5g, 127 mmol) and 1-boc-piperazine (11. 8 g, 63 mmol). The reaction mixture was allowed to reflux for 2 days then cooled to room temperature and filtered to remove potassium carbonate. Solvent from the mother liquor was removed under vacuum and the residue was purified by column chromatography on silica using 10% ethyl acetate/hexanes as the eluent (Rf= 0.3) to give 11b (15.8, 45 mmol, 71% yield). MS: calc. for Cl9H27FN203 : 350.2 ; Found: 351.0 (M+H); retention time: 2.24 minutes; Method info: APCI positive ion scan 100-1000 Frag V = 80; 95% 0.05% TFA/H20 to 95% ACN/0.05% TFA over 2 min, 3.4 min run, ODS-AQ column.

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, 2,3-Difluorobenzonitrile, other downstream synthetic routes, hurry up and to see.

Reference:
Patent; NEUROCRINE BIOSCIENCES, INC.; WO2005/42516; (2005); A2;,
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A common compound: 610-66-2, name is 2-(2-Nitrophenyl)acetonitrile, belongs to nitriles-buliding-blocks compound, it can change the direction of chemical reaction, and react with certain compounds to generate new functional products. A new synthetic method of this compound is introduced below. 610-66-2

General procedure: A mixture of aromaticaldehyde 1 (10 mmol), active methylene compound2 (10 mmol), and nano-ZnO catalyst (5 mol %) inaqueous ethanol (10 mL) was stirred under refl ux. Theformation of the products was monitored by TLC. Aftercompletion of the reaction (by TLC), the mixture wascooled to room temperature and fi ltered. The fi ltratewas concentrated to obtain a crude product, which waspurifi ed by recrystallization from aqueous ethanol.

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, 610-66-2, other downstream synthetic routes, hurry up and to see.

Reference:
Article; Alam, M. M.; Asiri, Ya. I.; Sulthana, S. Sh.; Tasqeeruddin, S.; Russian Journal of Organic Chemistry; vol. 56; 2; (2020); p. 315 – 321;,
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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 591769-05-0 as follows. 591769-05-0

To a solution of 4-iodo-lH-pyrazole 34e (0.72 g, 3.75 mmol) in acetonitrile (10 mL) was added 3-cyclopentylacrylonitrile 34c (0.5 g, 4.12 mmol) and DBU (0.57 g, 3.75 mmol). The reaction mixture was stirred at room temperature and concentrated in vacuum. The residue obtained was dissolved in ethyl acetate washed with 1 N aqueous HC1, brine, dried and concentrated in vacuum to furnish crude as oil. The crude was purified by flash column chromatography (silica gel 24 g, eluting with 0-50percent ethyl acetate in hexane) to furnish 3- cyclopentyl-3-(4-iodo-lH-pyrazol-l-yl)propanenitrile 34f (0.845 g, 72percent) as a colorless oil;1HNMR (300 MHz, DMSO) delta 8.06 (d, J= 0.6, 1H), 7.61 (s, 1H), 4.40 (td, J= 5.2, 9.0, 1H), 3.20 – 3.04 (m, 2H), 2.39 – 2.21 (m, 1H), 1.74 (m, 1H), 1.63 – 1.36 (m, 4H), 1.33 – 1.18 (m, 2H), 1.13 – 1.02 (m, 1H).

According to the analysis of related databases, 591769-05-0, the application of this compound in the production field has become more and more popular.

Reference:
Patent; BIOCRYST PHARMACEUTICALS, INC.; BABU, Yarlagadda S.; KOTIAN, Pravin L.; KUMAR, V. Satish; WU, Minwan; LIN, Tsu-Hsing; WO2011/31554; (2011); A2;,
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