Month: March 2021

Electric Literature of 455-18-5,Some common heterocyclic compound, 455-18-5, name is 4-(Trifluoromethyl)benzonitrile, molecular formula is C8H4F3N, 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 Example 1] Preparation of Compound III-2a [Show Image][Step H] Selenium powder (3.95 g, 50 mmol) was added to ethanol (50 mL) under nitrogen atmosphere. Then, sodium borohydride (2.02g, 53 mmol) wascautiouslyaddedslowlyfor30minutes (Hydrogen gas was produced.). To the resultant ethanolic sodium hydrogen selenide, 4-(trifluoromethyl)benzonitrile (11.9 g, 70 mmol) and pyridine (8 mL) were added. Then, 2 M hydrochloric acid (25 mL) was slowly added dropwise for 1. 5 hours while refluxing at 80 C. After further stirring for about 30 minutes, the precipitated target compound was filtered and washed with hexane and water. Recrystallization using benzene solvent yielded Compound III-2a (15.1 g, yield: 91 %) as yellow solid. 1H NMR (300 MHz, CDCl3) delta 11.07 (b, 1H), 10.43 (b, 1H), 7.99 (d, 2H, J = 8.5 Hz), 7.77 (d, 2H, J = 8.3 Hz).

These compound has a wide range of applications. It is believed that with the continuous development of the source of the synthetic route 4-(Trifluoromethyl)benzonitrile, its application will become more common.

Reference:
Patent; SNU R & DB Foundation; EP2540711; (2013); A1;,
Nitrile – Wikipedia,
Nitriles – Chemistry LibreTexts

Adding a certain compound to certain chemical reactions, such as: 368-77-4, name is 3-(Trifluoromethyl)benzonitrile, 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 368-77-4, Product Details of 368-77-4

A suspension of 3-(trifluoromethyl)benzonitrile (16c) (2.35 mL, 17.53 mmol, 1.00 equiv), hydroxylamine hydrochloride (1.58 g, 22.79 mmol, 1.30 equiv) and sodium carbonate (2.42 g, 22.79 mmol, 1.30 equiv) in ethanol (abs, 20 mL) was heated to reflux for 22 h. After 3 h, further hydroxylamine hydrochloride (1.30 equiv) and sodium carbonate (1.30 equiv) were added. The inorganic solids were removed by filtration and the solvent was removed in vacuum to give 3.60 g of a colorless oil that solidifies over time (quant.). 26 1H NMR (250 MHz, CDCl3): delta = 7.90 (s, 1H, 2H-ph-CF3), 7.82 (d, 1H, 3J = 7.8 Hz, 4H-ph-CF3), 7.68 (d, 1H, 3J = 7.8 Hz, 6H-ph-CF3), 7.53 (t, 1H, 3J = 7.8 Hz, 5H-ph-CF3), 4.92 (br s, 2H, NH2), 1.89 (s, 1H, -OH); ESI-MS: m/z = 204.6 [M+H]+.

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:
Article; Flesch, Daniel; Gabler, Matthias; Lill, Andreas; Gomez, Roberto Carrasco; Steri, Ramona; Schneider, Gisbert; Stark, Holger; Schubert-Zsilavecz, Manfred; Merk, Daniel; Bioorganic and Medicinal Chemistry; vol. 23; 13; (2015); p. 3490 – 3498;,
Nitrile – Wikipedia,
Nitriles – Chemistry LibreTexts

Adding a certain compound to certain chemical reactions, such as: 939-80-0, name is 4-Chloro-3-nitrobenzonitrile, 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 939-80-0, name: 4-Chloro-3-nitrobenzonitrile

[0188] A solution of 4-(2,4-difluorophenoxy)piperidine (0.640 g, 3 mmol), 4-chloro-3- mtrobenzomtriie (0.657 g, 3.60 mmol), and K2CO3 (0.829 g, 6.00 mmol) in DMSO (9.09 mL) was stirred at 80C overnight. The reaction mixture was subsequently partitioned between EtOAc and water. The organic layer was washed twice with water and dried over anhydrous NaiSO-t. The solvent was evaporated to give the title compound as an off-white solid, which was used without further purification. ESI-MS m/z [M+H] 360.2.

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; TAKEDA PHARMACEUTICAL COMPANY LIMITED; GREEN, Jason; HOPKINS, Maria; JONES, Benjamin; KIRYANOV, Andre A.; KUEHLER, Jon; MONENSCHEIN, Holger; MURPHY, Sean; NIXEY, Thomas; SUN, Huikai; (300 pag.)WO2018/183145; (2018); A1;,
Nitrile – Wikipedia,
Nitriles – Chemistry LibreTexts

Synthetic Route of 67832-11-5, A common heterocyclic compound, 67832-11-5, name is 4-Bromo-2-methylbenzonitrile, molecular formula is C8H6BrN, 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.

EXAMPLE 164A 4′-methoxy-3-methyl-1,1′-biphenyl-4-carbonitrile 4-Bromo-2-methylbenzonitrile (4.9 g, 25.0 mmol), Pd(PPh3)4 (578 mg) in benzene (50 mL) and 2.0 M aqueous solution of Na2CO3 (25 mL, 50.0 mmol) was treated with 4-methoxyphenylboronic acid (4.56 g, 30.0 mmol) in ethanol (20 mL) and heated at 75 C. for 17 hours. The mixture was allowed to cool to room temperature and the phases were separated. The aqueous phase was extracted with diethyl ether (3*40 mL). The original benzene layer and the diethyl ether extracts were combined, filtered over celite, dried over sodium sulfate, and filtered. The filtrate was concentrated under reduced pressure and the residue was purified by chromatography over silica using a mixture of hexane/CH2Cl2 (3:1) to provide the title compound as a white powder (5.73 g, 85 % yield). 1H-NMR (300 MHz, CDCl3) delta 2.35 (3H), 3.70 (s, 3H), 6.80-7.50 (m, 7H); MS (DCI) m/z 224 (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; Bennani, Yousseff L.; Faghih, Ramin; Dwight, Wesley J.; Vasudevan, Anil; Conner, Scott E.; US2002/137931; (2002); A1;,
Nitrile – Wikipedia,
Nitriles – Chemistry LibreTexts

Adding a certain compound to certain chemical reactions, such as: 939-79-7, name is 4-Methyl-3-nitrobenzonitrile, 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 939-79-7, category: nitriles-buliding-blocks

Dissolve sodium metal (0.345 g) in absolute EtOH (25 mL), add diethyloxalate (10 mL) and then add 4-methyl-3-nitrobenzonitrile (lb, m=0, 1.6 g, Aldrich) as an EtOH solution (25 mL). Stir the reaction mixture at rt for 16 hours, neutralize the reaction by addition of 5N HC1 (3 mL) and remove the EtOH under reduced pressure. Partition the residue between CH2C12 (100 mL) and H20 (50 mL). Wash the organic layer successively with H20 (50 mL) and brine (50 mL), dry (MgSO4) and concentrate to give a crude oil. Purify the oil by chromatography on SiO2 eluting with cyclohexane-EtOAc, 70-30 v/v, to afford gave after drying (40C, house vacuum), the title compound (1.5 g) as yellow crystals, mp 118 C.

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; AVENTIS PHARMACEUTICALS INC.; WO2006/23467; (2006); 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 90110-98-8 as follows. Recommanded Product: 90110-98-8

1.4 (Z)-3-bromo-N’-hydroxy-4-hydroxymethyl benzamidine (1-3) Hydroxylamine hydrochloride (0.524 g, 7.54 mmol) and sodium bicarbonate (1.27 g, 15.08 mmol) were added successively to a solution of 3-bromo-4-hydroxymethyl benzonitrile (1-2, 0.80 g, 3.77 mmol) in methanol (120 mL) to obtain a suspension which was then heated to reflux for 5 hours. It was then cooled down to room temperature and filtered. The filter cake was washed with methanol (10 mL), and the filtrate was concentrated to obtain 3-bromo-N’-hydroxy-4-hydroxymethyl benzamidine which was a white crude product (1-3, 0.90 g, 97% yield), which was directly used in the next step. The molecular ion peak shown by liquid chromatography-mass spectrometry was: MS (ESI): m/z 245/247 [M+H]+.

According to the analysis of related databases, 90110-98-8, the application of this compound in the production field has become more and more popular.

Reference:
Patent; SUZHOU CONNECT BIOPHARMACEUTICALS, LTD.; ZHENG, Wei; PAN, Wubin; YANG, Xin; (47 pag.)EP3048103; (2016); A1;,
Nitrile – Wikipedia,
Nitriles – Chemistry LibreTexts

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. 873-74-5, name is 4-Aminobenzonitrile, This compound has unique chemical properties. The synthetic route is as follows., Application In Synthesis of 4-Aminobenzonitrile

General procedure: A mixture of amine 1 (0.50 mmol), 1,3-diketone 2 (0.60 mmol, 1.2 equiv), iodine(12.7 mg, 0.05 mmol, 10 mol%) and TsOHH2O (19.0 mg, 0.10 mmol, 20 mol%) in 1,4-dioxane (3 mL) was added into a Schlenk flask (25 mL) and stirred at room temperature.The mixture was stirred at 140 C until the reaction was finished. Then, the solvent wasevaporated under reduced pressure and the residue was purified by column chromatography(petroleum ether/ethyl acetate 5:1 to 2:1) to afford the product 3.

According to the analysis of related databases, 873-74-5, the application of this compound in the production field has become more and more popular.

Reference:
Article; Zhou, Xiao-Yu; Chen, Xia; Yang, Dan; Synthetic Communications; vol. 50; 2; (2020); p. 177 – 184;,
Nitrile – Wikipedia,
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These common heterocyclic compound, 654-70-6, name is 4-Cyano-3-trifluoromethylaniline, 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. Recommanded Product: 4-Cyano-3-trifluoromethylaniline

To a solution of 4-amino-2- (trifluoromethyl) benzonitrile(XVII-I) (1.6 eq.) in THF (8.5 mL x mmol), cooled at -100C,LHMDS (4.5 eq.) was added drop wise. The reaction mixture was than stirred at this temperature for 40 min and HMPA(10% of the total THF) was added to the solution. After 5 min stirring, a solution of the ester XVIII-I (1 eq.) in THF (7 mL x mmol) was added to the reaction mixture. After 30 min at -100C, the solution was stirred 12h at room temperature. The reaction mixture was than quenched with 0. IN HCl and extracted with EtOAc. The crude material was purified by silica gel column chromatography. Yields range from 60 to 80%.(.R) -XXIV-3: 1H NMR (400 MHz, CDCl3) : 8.53 (broad s, IH) 7.63-7.72 (m, 2H), 7.50-7.55 (m, IH), 7.34-7.40 (m, 2H), 7.15-7.19 (m, 5H), 6.87 (dd, J= 8.8 Hz, IH) 3.87 (d, J= 14.4 Hz, IH), 3.45 (s, IH) . 3.22 (d, J= 13.6Hz, IH), 3.11 (d, J= 13.6Hz, IH), 2.95 (d, J= 14.4Hz, IH, CH2) . 13C NMR (100 MHz, CDCl3) Relevant: 172.1, 161.8 (d, J= 248Hz) 141.0,135.8, 134.5, 134.2 (d, J= 8.5Hz), 130.5, 128.8, 127.7, 122.6 (q) , 122.0, 117.6 (q, J= 5Hz) , 116.5 (d, J= 22.1Hz) 115.6, 105.0.

The synthetic route of 4-Cyano-3-trifluoromethylaniline has been constantly updated, and we look forward to future research findings.

Reference:
Patent; CONSIGLIO NAZIONALE DELLE RICERCHE; ISTITUTO SCIENTIFICO ROMAGNOLO PER LO STUDIO E LA CURA DEI TUMORI (I.R.S.T.) S.R.L.; VARCHI, Greta; TESEI, Anna; GUERRINI, Andrea; BRIGLIADORI, Giovanni; WO2010/116342; (2010); A2;,
Nitrile – Wikipedia,
Nitriles – Chemistry LibreTexts

Application of 33143-29-2, 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. 33143-29-2 name is 2,2-Dimethyl-2H-chromene-6-carbonitrile, 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: For NaIO4/imidazole system, the reaction was carried out with alkene (1 mmol), n-nonane (internal standard, 1 mmol), NaIO4 (2 mmol) and the catalyst (5% mmol) at 25 C for 5 h in the 2:1 mixture of acetonitrile : water. The catalyst was precipitated from the reaction mixture by adding hexane (10 mL), and then the organic phase was separated and purified on a silica gel column, and then analyzed by GC. The progress of the reaction was monitored by GC to find the optimal conversion and selectivity.

At the same time, in my other blogs, there are other synthetic methods of this type of compound, 2,2-Dimethyl-2H-chromene-6-carbonitrile, and friends who are interested can also refer to it.

Reference:
Article; Huang, Jing; Liu, Sirui; Ma, Yan; Cai, Jiali; Journal of Organometallic Chemistry; vol. 886; (2019); p. 27 – 33;,
Nitrile – Wikipedia,
Nitriles – Chemistry LibreTexts

Application of 17417-09-3, 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. 17417-09-3, name is 2-Fluoro-5-nitrobenzonitrile, This compound has unique chemical properties. The synthetic route is as follows.

General procedure: A mixture of benzonitrile 1 (10.0 mmol) and methylhydrazine (2.8 mL, 50.0 mmol) in EtOH (10.0 mL) was heated to reflux overnight. The mixture was cooled to rt and then concentrated. H2O (10.0 mL) and EtOAc (20.0 mL) were added to the residue. The organic layer was washed with H2O (10.0 mL), brine (10.0 mL), dried over Na2SO4, filtered, and concentrated in vacuo. The residue was subjected to silica-gel chromatography by using EtOAc/hexanes (1:1) as eluent to give the product 2.

The chemical industry reduces the impact on the environment during synthesis 2-Fluoro-5-nitrobenzonitrile. I believe this compound will play a more active role in future production and life.

Reference:
Article; Liu, Han-Jun; Hung, Shiang-Fu; Chen, Chuan-Lin; Lin, Mei-Huey; Tetrahedron; vol. 69; 19; (2013); p. 3907 – 3912;,
Nitrile – Wikipedia,
Nitriles – Chemistry LibreTexts