Month: June 2021

Electric Literature of 3939-09-1, A common heterocyclic compound, 3939-09-1, name is 2,4-Difluorobenzonitrile, molecular formula is C7H3F2N, 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 NaH (1.2 g, 30 mmol) in toluene (50 mL) was added but-3-en-1- ol (1.8 g, 25 mmol) dropwise and the mixture was allowed to stir at room temperature for 30 minutes. 2,4-Difluorobenzonitrile (4.2 g, 30 mmol) was then added in one portion and themixture was allowed to stir at room temperature for 6 hours. Water (30 mL) was slowly added and the mixture was extracted with EtOAc and washed with brine. The organic layer was dried over anhydrous sodium sulfate and concentrated in vacuo. The crude residue was purified using flash column chromatograpy on silica gel (20:1 PE:EtOAc) to provide compound Tnt-2b (4.2 g, 78%) as a yellow oil. ?H NMR (400 MHz, CDC13) 7.51-7.53 (m, 1H), 7.20-7.25 (m, 1H), 6.79-6.81 (m, 1H), 5.85-5.89 (m, 1H), 5.05-5.11 (m, 2H), 4.05-4.11 (m, 2H), 2.47-2.5 1 (m, 2H)

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; MERCK SHARP & DOHME CORP.; REGER, Thomas; WALJI, Abbas; SANDERS, John; WAI, John; WANG, Liping; WO2014/11769; (2014); A1;,
Nitrile – Wikipedia,
Nitriles – Chemistry LibreTexts

Adding a certain compound to certain chemical reactions, such as: 53312-81-5, name is 5-Amino-2-fluorobenzonitrile, 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 53312-81-5, SDS of cas: 53312-81-5

To a solution of 5-amino-2-fluorobenzonitrile (3.75 g) and Et3N (4.22 mL) in CH2Cl2 (100 mL) was added ethyloxalyl chloride (3.08 mL) in a dropwise fashion over 10 minutes. The reaction was stirred at RT under N2 for 1.5 h. The reaction mixture was washed with water (2×50 mL) and brine (1×50 mL), filtered through phase separatory paper and evaporated. The residue was dissolved in 20 mL of CH2Cl2 and 100 mL of hexane was added. The solution was allowed to stand at RT for the weekend. The precipitate was filtered, rinsed with hexane, and dried under vacuum to give 5.43 g of 1-(3-cyano-4-fluorophenyl)-oxoacetic acid ethyl ester. 1H NMR (CDCl3) delta1.44 (t, 3H, J=7.2 Hz, OCH2CH3), 4.44 (q, 2H, J=7.0 Hz, OCH2CH3), 7.26 (t, 1H, J=3.8 Hz, aromatic H), 7.82 (m, 1H, aromatic H), 8.04 (m, 1H, aromatic H), 8.97 (bs, 1H, NH). DCI mass spectrum z (rel. intensity) 237.1 (M+H, 6.6), 254.0 (M+Na, 100).

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

Reference:
Patent; DuPont Pharmaceuticals Company; US6339099; (2002); B1;,
Nitrile – Wikipedia,
Nitriles – Chemistry LibreTexts

Synthetic Route of 5332-06-9, The chemical industry reduces the impact on the environment during synthesis 5332-06-9, name is 4-Bromobutanenitrile, I believe this compound will play a more active role in future production and life.

Reference Example 1 4-(p-tolylamino)butanenitrile p-Toluidine (10.407 g, 97.116 mmol) was dissolved in anhydrous acetonitrile and, after adding potassium carbonate (49.9 g, 361.272 mmol), stirred at room temperature for 10 minutes. After slowly adding 4-bromobutyronitrile (10.1 mL, 101.972 mmol) to the resultant reaction mixture, reaction was carried out at 100 C. for 2 days. The mixture was cooled to room temperature and the produced solid was removed by filtering. The filtrate was concentrated under reduced pressure. A target compound (13.23 g, 78.2%) was yielded. A target compound was used in the next step without further purification. 1H NMR (CDCl3, 300 MHz) delta 7.04 (d, J=8.0 Hz, 2H), 6.57 (d, J=8.3 Hz, 2H), 3.62 (s, 1H, NH), 3.29 (q, J=6.3 Hz, 2H), 2.47 (t, J=7.0 Hz, 2H), 2.28 (s, 3H), 1.96 (t, J=6.8 Hz, 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, 4-Bromobutanenitrile, other downstream synthetic routes, hurry up and to see.

Reference:
Patent; Korea Institute of Science and Technology; US2011/319619; (2011); 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 98730-77-9 as follows. Recommanded Product: 98730-77-9

Step 2. Preparation of 1-((1,3-dioxoisoindolin-2 yl)methyl)cyclopropanecarbonitrile A solution of 1-(hydroxymethyl)-cyclopropanecarbonitrile (5.52 g, 56.8 mmol), phthalimide (9.20 g, 62.5 mmol), and triphenylphosphine (16.4 g, 62.5 mmol) in THF (550 mL) was treated with DEAD (9.90 mL, 62.5 mmol) and stirred at room temperature for 17 hours. The reaction mixture was then concentrated and the resulting solids were triturated in diethyl ether (150 mL), and collected by filtration. Purification by flash chromatography (SiO2, 0-20% EtOAc in DCM) afforded 1-((1,3-dioxoisoindolin-2-yl)methyl)-cyclopropanecarbonitrile (8.8 g, 38.8 mmol, 68%) as a white solid: LCMS(m/z) 227.0 (MH+), tR=0.66 minute; 1H NMR (300 MHz, CDCl3) delta 7.90 (dd, J=5.4, 3.1 Hz, 2H), 7.77 (dd, J=5.4, 3.1 Hz, 2H), 3.81 (s, 2H), 1.30-1.44 (m, 2H), 1.28 (d, J=3.8 Hz, 2H).

According to the analysis of related databases, 98730-77-9, the application of this compound in the production field has become more and more popular.

Reference:
Patent; Costales, Abran Q.; Huang, Shenlin; Jin, Jeff (Xianming); Liu, Zuosheng; Pecchi, Sabina; Poon, Daniel; Tellew, John; US2011/52578; (2011); A1;,
Nitrile – Wikipedia,
Nitriles – Chemistry LibreTexts

Electric Literature of 10406-25-4, A common heterocyclic compound, 10406-25-4, name is 4-(Aminomethyl)benzonitrile, molecular formula is C8H8N2, 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 round-bottom flask equipped with a stir bar was added 17a-b (1.0 eq), Boc2O (1.1 eq), CH2Cl2 (10mL/mmol), and triethylamine (1.5 eq). The reaction mixture was stirred at room temperature overnight. The reaction was concentrated in vacuo and partitioned between ethyl ether and 1M HCl. The organic layer were separated, washed with saturated NaHCO3 and brine, dried over MgSO4, and concentrated in vacuo to give a white crystalline solid. 4.2.4.2 128 tert-Butyl (4-cyanobenzyl)carbamate (18a) Yield: 93%. MP: 114-116C. 1H NMR (400MHz, CDCl3) delta 7.62 (d, J=7.9Hz, 2H, -ArH), 7.39 (d, J=8.5Hz, 2H, -ArH), 4.96 (s, 1H, -NH-), 4.37 (d, J=5.9Hz, 2H, -CH2-), 1.46 (s, 9H, -CH3)

The synthetic route of 10406-25-4 has been constantly updated, and we look forward to future research findings.

Reference:
Article; Luo, Zonghua; Rosenberg, Adam J.; Liu, Hui; Han, Junbin; Tu, Zhude; European Journal of Medicinal Chemistry; vol. 150; (2018); p. 796 – 808;,
Nitrile – Wikipedia,
Nitriles – Chemistry LibreTexts

Adding a certain compound to certain chemical reactions, such as: 403-54-3, name is 3-Fluorobenzonitrile, 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 403-54-3, Product Details of 403-54-3

a. 3-Cyano-4-nitrofluorobenzene m-Fluorobenzonitrile (96.8 g., 0.8 mole) is added in two and one-half hours to a mixture of concentrated sulfuric acid (600 ml.) and potassium nitrate (80.9 g., 0.8 mole) at 3-6 C., then allowed to warm to 25 C. The mixture is poured over cracked ice (3000 ml.), extracted with chloroform (5*250 ml.), dried and the solvent removed. The residue is extracted with pentane and dried to give 3-cyano-4-nitrofluorobenzene (115 g., 86.5%) m.p. 102-104 C.

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

Reference:
Patent; Rohm and Haas Company; US31455; (1983); E1;,
Nitrile – Wikipedia,
Nitriles – Chemistry LibreTexts

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. 17626-40-3, name is 3,4-Diaminobenzonitrile, A new synthetic method of this compound is introduced below., Formula: C7H7N3

3,4-diaminobenzonitrile (42, 2.5g; 18.75mmol; 1.0 equiv) was dissolved in 5M 55 aqueous HCl (110mL). The mixture was heated at 105C to reflux for 12h. After stopping the reaction, the mixture was cooled to room temperature, basified with aqueous ammonia and stored overnight. The generated solid 56 product was collected by filtration and washed with ice water. The products could be used without further purification. Yield: 2.5g (94.0%). 1H NMR (300MHz, DMSO) delta 12.47 (s, 1H), 8.34 (s, 1H), 8.03 (s, 1H), 7.62 (d, J=4.17Hz, 1H), 7.45 (d, J=8.34Hz, 1H). MS m/z: 144.2 [M+ H] +.

The synthetic route of 17626-40-3 has been constantly updated, and we look forward to future research findings.

Reference:
Article; Xu, Li-Li; Wu, Yu-Feng; Wang, Lei; Li, Cui-Cui; Li, Li; Di, Bin; You, Qi-Dong; Jiang, Zheng-Yu; European Journal of Medicinal Chemistry; vol. 157; (2018); p. 1376 – 1394;,
Nitrile – Wikipedia,
Nitriles – Chemistry LibreTexts

Related Products of 114897-91-5,Some common heterocyclic compound, 114897-91-5, name is 2-(4-Bromo-2-fluorophenyl)acetonitrile, molecular formula is C8H5BrFN, 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 Mel (3.2 mL, 49.3 mmol) in anhydrous DMF (82 mL) at 0 C. was added NaH (60%, 2.0 g), followed by (4-bromo-2-fluorophenyl)acetonitrile (3.5 g, 16.4 mmol). The mixture was slowly warmed up to room temperature and stirred for 3 hours. The reaction was quenched by the addition of saturated NH4Cl and extracted with EtOAc (3×150 mL). The combined organic extracts were washed with brine, dried with Na2SO4 and evaporated to dryness. The mixture was purified by flash column chromatography (0-20% EtOAc in hexanes) to give the product (3.0 g, 77% yield). 1H NMR (300 MHz, CDCl3) delta: 1.78 (s, 6H), 7.26-7.42 (m, 3H).

These compound has a wide range of applications. It is believed that with the continuous development of the source of the synthetic route 2-(4-Bromo-2-fluorophenyl)acetonitrile, its application will become more common.

Reference:
Patent; Agouron Pharmaceuticals, Inc.; US2005/176701; (2005); A1;,
Nitrile – Wikipedia,
Nitriles – Chemistry LibreTexts

2042-37-7, name is 2-Bromobenzonitrile, 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. Computed Properties of C7H4BrN

Example 2 2M Sodium carbonate solution (200 ml) was added to a stirred mixture of 4-methylphenylboronic acid (30 g), 2-bromobenzonitrile (36.4 g), palladium (II) chloride (0.4 g), methanol (200 ml) and toluene (200 ml) at 5C. The temperature rose to approximately 20C and a solid precipitated. The reaction mixture was then heated at reflux for 2 hours. The reaction mixture was allowed to cool and water (100 ml) was added, followed by diatomaceous earth (5 g). The mixture was stirred for 15 minutes, then filtered through diatomaceous earth. The organic phase of the filtrate was separated and washed with 2M sodium carbonate solution and then water. The organic phase was then filtered and the filtrate evaporated. The resultant solid was recrystallized from petroleum ether (b.p. 110-120C) to give 4–methylbiphenyl-2-carbonitrile (in 80% yield) identical to that obtained in Example 1.

The synthetic route of 2042-37-7 has been constantly updated, and we look forward to future research findings.

Reference:
Patent; ZENECA LIMITED; EP470795; (1992); A1;,
Nitrile – Wikipedia,
Nitriles – Chemistry LibreTexts

Application of 3441-01-8,Some common heterocyclic compound, 3441-01-8, name is 3-Cyanobenzamide, molecular formula is C8H6N2O, 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.

The precipitated crystals were collected through filtration, washed with water, and dried, to thereby obtain 4.78 g of m-cyanobenzoic acid (yield 94percent, based on m-cyanobenzamide). The m-cyanobenzoic acid obtained had a purity of 98percent.

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

Reference:
Patent; Showa Denko Kabushiki Kaisha; US6433211; (2002); B1;,
Nitrile – Wikipedia,
Nitriles – Chemistry LibreTexts