Month: December 2020

1080-74-6, name is 2-(3-Oxo-2,3-dihydro-1H-inden-1-ylidene)malononitrile, belongs to nitriles-buliding-blocks compound, is considered to be a conventional heterocyclic compound, which is widely used in drug synthesis. The chemical synthesis route is as follows. 1080-74-6

Take a two-necked round bottom flask, dissolve compound 8-1 in chloroform, and perform a Knoevenagel condensation reaction with malononitrile indanone ketone electronic unit under weakly basic conditions. After TLC monitors the reaction, directly use reaction oil The ether / dichloromethane eluent was passed through the column to obtain the final type of organic solar cell using diindenobisthiophene as the core; wherein, the compound 8-1, the electron-drawing unit, pyridine, and chloroform had a ratio of 0.2 to 2.2mmol: 0.3 3.0mmol: 0.01 0.5mmol: 10 50mL; yield is 84.7%;

Statistics shows that 1080-74-6 is playing an increasingly important role. we look forward to future research findings about 2-(3-Oxo-2,3-dihydro-1H-inden-1-ylidene)malononitrile.

Reference:
Patent; Xiamen University; Xie Suyuan; Zheng Shanyu; An Mingwei; Pei Yaqian; Deng Linlong; (31 pag.)CN110746440; (2020); A;,
Nitrile – Wikipedia,
Nitriles – Chemistry LibreTexts

25808-30-4, 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. 25808-30-4 name is 2-(Methylamino)acetonitrile hydrochloride, 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.

[Example 50] Preparation of 3-methyl-1-(4-methylbenzyl)-4-(4-phenoxyphenyl)iminoimidazolidine-2-one (I-363) To a mixture of 4-methylbenzylamine hydrochloride (10 g, 83 mmol) and N,N-dimethylacetamide (50 mL) was added 1,1′-carbonyldiimidazole (14.05 g, 87 mmol) under ice-cooling. To the mixture was added DBU (18.66 mL, 124 mmol), and the resulting mixture was stirred at 0¡ãC for 30 minutes. To the reaction mixture was added 2-(methylamino)acetonitrile hydrochloride (10.55 g, 99 mmol) under ice-cooling. Further, to the mixture was added DBU (24.88 mL, 165 mmol) under ice-cooling, and the resulting mixture was stirred at room temperature for 45 minutes and stirred at 50¡ãC for additional 90 minutes. To the reaction mixture was added water (500 mL). The mixture was extracted with ethyl acetate (500 mL*2), washed by brine (500 mL), dried over anhydrous magnesium sulfate, and concentrated in vacuo. The resulting residue was purified by silica gel column chromatography (methanol/chloroform) to give 4-imino-3-methyl-1-(4-methylbenzyl)imidazolidine-2-one (9.43 g, Yield:52percent) as yellow solid. 1H-NMR (delta ppm TMS/CDCl3): 2.31 (3H, s), 2.94 (3H, s), 3.93 (2H, s), 4.66 (2H, s), 6.90 (1H, br.s), 7.11 (2H, d, J=8.2 Hz), 7.27 (2H, d, J=8.2 Hz).

At the same time, in my other blogs, there are other synthetic methods of this type of compound, 2-(Methylamino)acetonitrile hydrochloride, and friends who are interested can also refer to it.

Reference:
Patent; Shionogi & Co., Ltd.; KAI, Hiroyuki; ENDOH, Takeshi; JIKIHARA, Sae; ASAHI, Kentaro; HORIGUCHI, Tohru; EP2604260; (2013); A1;,
Nitrile – Wikipedia,
Nitriles – Chemistry LibreTexts

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 939-80-0 as follows. 939-80-0

In a reactor, compound 2 (917 mg, 2.0 mmol), compound 4 (274 mg, 3.0 mmol) and Cs2CO3 (325 mg, 1.0 mmol) were added to dry THF (20 mL). Then the reactor was sealed under nitrogen, and the mixture was kept at 30 C., stirred for 12 hours. After the reaction, the mixture was diluted with dichloromethane (10 mL) and then filtered. The resulting filtrate was washed twice with water (2¡Á10 mL), and aqueous phases were combined, then the combined aqueous phases were extracted twice with dichloromethane (2¡Á10 mL). The organic layers were combined, dried over Na2SO4, and concentrated to obtain compound XVII as a light yellow powder (1004 mg, yield 90.2%), HPLC purity: 99.2%.

According to the analysis of related databases, 939-80-0, the application of this compound in the production field has become more and more popular.

Reference:
Patent; XU, YONG; (10 pag.)US2016/257667; (2016); A1;,
Nitrile – Wikipedia,
Nitriles – Chemistry LibreTexts

A common heterocyclic compound, 1897-41-2, name is 2,3,5,6-Tetrachloroterephthalonitrile, molecular formula is C8Cl4N2, 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. 1897-41-2.

0.60 g (0.015 mol) of sodium hydroxide was added to a solution of 1.22 g (0.0075 mol) of 3,5-dichloropyridin-4-amine in 40 mL of DMF, followed by addition of 2 g (0.0075 mol) of 2,3,5,6-tetrachloroterephthalonitrile under stirring, the mixture was stirred for 5 h after addition at room temperature. After the reaction was over by Thin-Layer Chromatography monitoring, the reaction mixture was poured into water and extracted with ethyl acetate, the organic phase was washed with water and saturated brine, dried over anhydrous magnesium sulfate, filtered and then concentrated under reduced pressure. The residue was purified through silica column (ethyl acetate/petroleum ether (boiling point range 60-90¡ã C.)=1:3, as an eluent) to give 2.16 g of compound C-124 as yellow solid, m.p. 202-204¡ã C. [0197] 1H-NMR (300 MHz, internal standard TMS, solvent CDCl3) delta (ppm): 7.28 (br, 1H, NH), 8.30 (s, 2H, Py-2,6-2H).

The synthetic route of 2,3,5,6-Tetrachloroterephthalonitrile has been constantly updated, and we look forward to future research findings.

Reference:
Patent; SHENYANG RESEARCH INSTITUTE OF CHEMICAL INDUSTRY CO., LTD.; SINOCHEM CORPORATION; Liu, Changling; Huang, Guang; Lan, Jie; Hao, Shulin; Li, Zhinian; Li, Huichao; Guan, Aiying; Jiang, Airu; Xu, Ying; US2014/213598; (2014); A1;,
Nitrile – Wikipedia,
Nitriles – Chemistry LibreTexts

127946-77-4, Name is 1-Amino-1-cyclopropanecarbonitrile hydrochloride, 127946-77-4, belongs to nitriles-buliding-blocks compound, is considered to be a conventional heterocyclic compound, which is widely used in drug synthesis. The chemical synthesis route is as follows.

A mixture of example 9a) (850 mg, 2.74 mmol, Eq: 1.00), 1-aminocyclopropane- carbonitrile hydrochloride (422 mg, 3.56 mmol, Eq: 1.30), sodium 2-ethylhexanoate (705 mg, 4.24 mmol, Eq: 1.55) in water (3 ml) and THF (2.00 ml) was stuffed at 55 C for 18 h. To the reaction mixture were added hydrochloric acid (189 mg, 157 tl, 1.91 mmol, Eq:0.70) and sodium chloride (1.36 g, 1.36 ml, 23.3 mmol, Eq: 8.50). The mixture was stuffed for 15 mm, then poured into AcOEt (25 ml) and extracted. The aqueous layer was back- extracted with AcOEt (3 x 20 ml). The organic layers were dried over Na2SO4 and concentrated in vacuo. The crude material was purified by flash chromatography (silica gel, 40 g, 0% to 90% EtOAc in heptane) to yield the title compound as white foam (560 mg;52 %). mlz = 393.0 [M+Hf?.

Statistics shows that 1-Amino-1-cyclopropanecarbonitrile hydrochloride is playing an increasingly important role. we look forward to future research findings about 127946-77-4.

Reference:
Patent; F. HOFFMANN-LA ROCHE AG; HOFFMANN-LA ROCHE INC.; ANSELM, Lilli; BANNER, David; HAAP, Wolfgang; KUHN, Bernd; LUEBBERS, Thomas; PETERS, Jens-Uwe; SPINNLER, Beat; WO2014/29722; (2014); A1;,
Nitrile – Wikipedia,
Nitriles – Chemistry LibreTexts

16532-79-9, 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. 16532-79-9, name is 4-Bromophenylacetonitrile, This compound has unique chemical properties. The synthetic route is as follows.

A solution of 4-Bromophenylacetonitrile (10.0 g, 51.0 mmol) in tetrahydrofuran (200 mL) was added slowly to a suspension of sodium hydride (60% in mineral oil, 6.0 g, 153 mmol) in tetrahydrofuran (400 mL) at room temperature over 30 minutes. After complete addition, methyl iodide (7.6 mL, 122 mmol) was added slowly over 30 minutes, maintaining the reaction temperature below 40 C. by occasional immersion into a water bath. The reaction was then stirred overnight at room temperature. The mixture was poured into water (500 mL) and extracted into ethyl acetate (2*300 mL). The combine organic layers were washed with brine (2*300 mL), dried over magnesium sulfate, filtered and concentrated. Crude purified on silica gel eluding with 2% ethyl acetate in hexanes) to give 2-(4-bromophenyl)-2-methylpropanenitrile (11 g, 96%) as a yellow oil. 1H NMR (300 MHz, CDCl3): delta ppm 1.70 (s, 6H), 7.35 (dd, 2H), 7.53 (dd, 2H).

If you are interested in these compounds, you can also browse my other articles.Thank you for taking the time to read this article. I hope you enjoyed it.

Reference:
Patent; pfizer Inc; US2010/197591; (2010); A1;,
Nitrile – Wikipedia,
Nitriles – Chemistry LibreTexts

21524-39-0, These common heterocyclic compound, 21524-39-0, name is 2,3-Difluorobenzonitrile, 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.

A mixture of 3 -methyl- lH-pyrazole-4-carboxylic acid ethyl ester (1.25 g, 8.1 1 mmol), potassium carbonate (1.68 g, 12.16 mmol), 2,3-difluorobenzonitrile (1.08 mL, 9.73 mmol) in dimethylformamide (12 mL) is heated at 100C with the aid of a magnetic stirred. After 2.5 hr. the reaction mixture is treated with water and extracted with ethyl acetate. The organic layer is decanted, washed with brine, dried over magnesium sulfate and the solvent evaporated under reduced pressure to give 2.3 g of l-(2-cyano-6-fluoro- phenyl)-3 -methyl- lH-pyrazole-4-carboxylic acid ethyl ester (this compound is contaminated with the other pyrazole regioisomer in a ratio 75:25). MS (m/z): 274 (M+1). A capped vial is charged with ethyl l-(2-cyano-6-fluoro-phenyl)-3-methyl- pyrazole-4-carboxylate (1.97 g, 7.21 mmol) (contaminated with the other pyrazole regioisomer in a ratio of 75:25, 1,2-ethanediamine, N-methyl- (6 mL, 68.02 mmol) and phosphorus pentasulfide (229 mg, 1,01 mmol) and the mixture is stirred at 1 10C for 30 min and then allow to reach rt. Solvent is evaporated in vacuo and the residue purified by normal phase Isco chromatography using dichloromethane/2M ammonia in methanol from 95/5 to 85/15 as eluent to yield 2.1 1 g of ethyl l-[2-fluoro-6-(l-methyl-4,5- dihydroimidazol-2-yl)phenyl]-3-methyl-pyrazole-4-carboxylate (contaminated with the other pyrazole regioisomer in a ratio 75:25). MS (m/z): 331 (M+1). Potassium permanganate (1.58 g, 10 mmmol) and montmorillonite K- 10 (3.16 g) are grounded together in a mortar until a fine homogeneous powder is obtained.KMn04-montmorillonite K-10 (3.2 g, 6.78 mmol) is added portionwise to a solution of ethyl l-[2-fluoro-6-(l-methyl-4,5-dihydroimidazol-2-yl)phenyl]-3-methyl-pyrazole-4- carboxylate (1.12 g, 3.39 mmol) (contaminated with the other pyrazole regioisomer in a ratio 75:25) in acetonitrile (84.76 mL, 1.62 moles). The mixture is stirred at room temperature for 6.5 hr. and more KMn04-montmorillonite K-10 (0.8 g, 1.69 mmol) is added portionwise and the mixture stirred at room temperature overnight. Ethanol is added and stirred for additional 20 min. Then the reaction mixture is filtered through a short pad of celite and the solid material is washed with acetonitrile. The solvent is evaporated under reduced pressure and the crude mixture is purified normal phase Isco chromatography using ethyl acetate as eluent to yield 518 mg of l-[2-fluoro-6-(l- methylimidazol-2-yl)phenyl]-3-methyl-pyrazole-4-carboxylate (contaminated with the other pyrazole regioisomer in a ratio 75:25). MS (m/z): 329 (M+1).

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 21524-39-0.

Reference:
Patent; ELI LILLY AND COMPANY; BENITO COLLADO, Ana Belen; DIAZ BUEZO, Nuria; JIMENEZ-AGUADO, Alma Maria; LAFUENTE BLANCO, Celia; MARTINEZ-GRAU, Maria Angeles; PEDREGAL-TERCERO, Concepcion; TOLEDO ESCRIBANO, Miguel Angel; WO2011/60217; (2011); A1;,
Nitrile – Wikipedia,
Nitriles – Chemistry LibreTexts

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. 3939-09-1, name is 2,4-Difluorobenzonitrile belongs to nitriles-buliding-blocks compound, it is a common compound, a new synthetic route is introduced below. 3939-09-1

4-Fluoro-2-(3-methyl-1H-1,2,4-triazol-1-yl)benzonitrile and 4-fluoro-2-(5-methyl-1H-1,2,4-triazol-1-yl)benzonitrile. A solution of 2,4-difluorobenzonitrile (7.07 g, 50.8 mmol) and 3-methyl-1H-1,2,4-triazole (4.22 g, 50.8 mmol) in N,N-dimethylformamide (45 ml) was treated with powdered anhydrous potassium carbonate (10 g) and the resulting mixture was stirred at 22 C. for 18 h. The solid was then filtered and the filtrate was concentrated in vacuo. The residue was diluted with ethyl acetate, washed with water and brine, dried over anhydrous magnesium sulfate and concentrated. The mixture containing the 2 and 4-triazolyl-benzonitriles was purified by a combination of chromatography on silica gel (elution gradient of ethyl acetate in hexane) and on reversed phase silica gel to give 1.86 g (18% yield) of 4-Fluoro-2-(3-methyl-1H-1,2,4-triazol-1-yl)benzonitrile and 0.526 g (5% yield) of 4-fluoro-2-(5-methyl-1H-1,2,4-triazol-1-yl)benzonitrile. 4-Fluoro-2-(3-methyl-1H-1,2,4-triazol-1-yl)benzonitrile. White crystals (ethyl acetate/hexanes). mp 117-118 C. 1HNMR 400 MHz (CDCl3) delta (ppm): 2.54 (3H, s, CH3), 7.24 (1H, m, CH), 7.62 (1H, dd, J=2.5 Hz and J=9.1 Hz, CH), 7.84 (1H, dd, J=5.6 Hz and J=8.6 Hz, CH), 8.82 (1H, s, CH). Anal. Calcd for C10H7FN4: C, 59.40; H, 3.49; N, 27.71. Found: C, 59.25; H, 3.32; N, 27.81. 4-fluoro-2-(5-methyl-1H-1,2,4-triazol-1-yl)benzonitrile. White crystals (ethyl acetate-hexane). mp 120-121 C. 1HNMR 400 MHz (CDCl3) delta (ppm): 2.56 (3H, s, CH3), 7.30 (1H, dd, J=2.5 Hz and J=8.1 Hz, CH), 7.39 (1H, m, CH), 7.91 (1H, dd, J=5.5 Hz and J=8.6 Hz, CH), 8.06 (1H, s, CH). Anal. Calcd for C10H7FN4: C, 59.40; H, 3.49; N, 27.71. Found: C, 59.35; H, 3.70; N, 27.77.

The synthetic route of 3939-09-1 has been constantly updated, and we look forward to future research findings.

Reference:
Patent; Bristol-Myers Squibb Company; US2007/129379; (2007); A1;,
Nitrile – Wikipedia,
Nitriles – Chemistry LibreTexts

3939-09-1, Name is 2,4-Difluorobenzonitrile, 3939-09-1, belongs to nitriles-buliding-blocks compound, is considered to be a conventional heterocyclic compound, which is widely used in drug synthesis. The chemical synthesis route is as follows.

To a solution of 2,4-difluorobenzonitrile (10 g, 72 mmol) dissolved in tetrahydrofuran (20 mL), and dimethylformamide (40 mL) was added 1,2,4-triazole sodium salt (6.3 g, 70 mmol) and the mixture stirred at 90 C. for 3 h after which the mixture was filtered and the solvent removed. The resulting residue was adsorbed onto silica gel and intermediates 67 and 68 separated by flash chromatography, eluting with 0% to 30% ethyl acetate/hexanes. 4-Fluoro-2-(1H-1,2,4-triazol-1-yl)benzonitrile. Colorless needles (2.46 g, 18% yield) 1H NMR (500 MHz, CDCl3) delta: 8.89 (1H, s), 8.19 (1H, s), 7.85 (1H, dd, J=8.7, 5.6 Hz), 7.60 (1H, dd, J=8.8, 2.4 Hz), 7.28-7.24 (1H, m). LCMS (M+H) calcd for C9H6N4F: 189.05. found: 189.13. 4-(1H-1,2,4-Triazol-1-yl)-2-fluorobenzonitrile. White solid (0.746 g, 6% yield) 1H NMR (500 MHz, CDCl3) delta: 8.66 (1H, s), 8.15 (1H, s), 7.79 (1H, dd, J=8.5, 6.7 Hz), 7.69 (1H, dd, J=9.5, 1.8 Hz), 7.65-7.63 (1H, m). LCMS (M+H) calcd for C9H6N4F: 189.05. found: 189.13. 4-Fluoro-2-(1H-1,2,4-triazol-1-yl)benzonitrile and 4-(1H-1,2,4-triazol-1-yl)-2-fluorobenzonitrile. To a solution of 2,4-difluorobenzonitrile (10 g, 72 mmol) dissolved in THF (20 mL), and DMF (40 mL) was added 1,2,4-triazole sodium (6.3 g, 70 mmol) and the mixture was stirred at 90 C. for 3 h, filtered and concentrated. The residue was adsorbed onto Silica gel and purified by flash chromatography eluting with 0%-10%-30% EtOAc/hexanes to give the 4-triazolyl isomer as colorless needles (2.46 g, 18%) and the 2-substituted isomer as a white solid (0.7455 g, 6%). 4-Fluoro-2-(1H-1,2,4-triazol-1-yl)benzonitrile. 1H NMR (500 MHz, CDCl3) delta: 8.89 (1H, s), 8.19 (1H, s), 7.85 (1H, dd, J=8.7, 5.6 Hz), 7.60 (1H, dd, J=8.8, 2.4 Hz), 7.28-7.24 (1H, m). LCMS (M+H) calcd for C9H6N4F: 189.05. found: 189.13. 4-(1H-1,2,4-triazol-1-yl)-2-fluorobenzonitrile. 1H NMR (500 MHz, CDCl3) delta: 8.66 (1H, s), 8.15 (1H, s), 7.79 (1H, dd, J=8.5, 6.7 Hz), 7.69 (1H, dd, J=9.5, 1.8 Hz), 7.65-7.63 (1H, m). LCMS (M+H) calcd for C9H6N4F: 189.05. found: 189.13.

Statistics shows that 2,4-Difluorobenzonitrile is playing an increasingly important role. we look forward to future research findings about 3939-09-1.

Reference:
Patent; Bristol-Myers Squibb Company; US2007/129379; (2007); A1;,
Nitrile – Wikipedia,
Nitriles – Chemistry LibreTexts

658-99-1, 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. 658-99-1, name is 2-(3,4-Difluorophenyl)acetonitrile, A new synthetic method of this compound is introduced below.

Under protective gas (argon), 125 mg (1.11 mmol) of potassium tert-butoxide were added to 1.006 g (5.55 mmol) of methyl (2E)-3-(5-fluoropyridin-3-yl)acrylate and 0.850 g (5.55 mmol) of (3,4-difluorophenyl)acetonitrile in 45.0 ml of toluene and 2 ml of DMF, and the mixture was stirred at 60 C. for 5 h. After removal of the solvent under reduced pressure, the residue was taken up in ethyl acetate and washed twice with in each case 50 ml of water. The combined organic phases were dried over sodium sulfate and the solvent was removed under reduced pressure. Chromatography of the residue over silica gel (ethyl acetate/heptane=15:85) gave 1.050 g (57% of theory) of the diastereomeric methyl 4-cyano-4-(3,4-difluorophenyl)-3-(5-fluoropyridin-3-yl)butanoates.

If you are interested in these compounds, you can also browse my other articles.Thank you for taking the time to read this article. I hope you enjoyed it.

Reference:
Patent; Bayer CropScience Aktiengesellschaft; MOSRIN, MARC; JAKOBI, HARALD; DIETRICH, HANSJOERG; GATZWEILER, ELMAR; ROSINGER, CHRISTOPHER HUGH; SCHMUTZLER, DIRK; (66 pag.)US2017/290330; (2017); A1;,
Nitrile – Wikipedia,
Nitriles – Chemistry LibreTexts