Month: November 2020

These common heterocyclic compound, 75344-77-3, name is 4-Bromo-3,5-dimethylbenzonitrile, 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. 75344-77-3

Step 1: 4-Bromo-3,5-dimethylbenzonitrile (0.5 g, 2.38 mmol) was dissolved in THF (12 ml). The solution was cooled in a dry ice/diethyl ether bath. N-butyllithium (1.05 ml 2.50M solution in hexanes, 2.62 mmol) was added slowly over 30 m. Dry N,Ndimethylformamide (0,26 ml, 3.3 mmol) was then added slowly and the reaction allowed to warm slowly. After 1 h the reaction appeared complete (LC/MS, TLC) and by 2 h with the temperature at -30 C, the reaction was neutralized by addition of an aqueous saturated sodium chloride solution. The mixture was taken up in ethyl acetate and water, the phaseswere separated, the aqueous phase was extracted once more with ethyl acetate, and the combined organics were washed with more saturated sodium chloride solution. After drying over sodium sulfate, flhration and evaporation, the residue was purified by silica gel chromatography (ethyl acetate/hexanes gradient) to give 4-formyl-3,5 -dimethylbenzonitrile as a white solid (0.18 g, 47%).

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 75344-77-3.

Reference:
Patent; GLOBAL BLOOD THERAPEUTICS, INC.; LI, Zhe; ZANCANELLA, Manuel; YU, Chul; SETTI, Lina; SHAM, Hing; XU, Qing; YEE, Calvin; YU, Ming; (402 pag.)WO2016/201052; (2016); A1;,
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21524-39-0, 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 21524-39-0 as follows.

3-Fluoro-2-(l,l-dioxo-llambda6-[l,2]thiazinan-2-yl)benzonitriQ. To a solution of l,l-dioxo-llambda6-[l,2]thiazin-2-ane (1.90 g, 14.4 mmol) dissolved in tetrahydrofuran (8 mL) and dimethylformamide (2 mL) was added sodium hydride (0.36 g, 95%, 14.4 mmol) and the mixture stirred for 20 min. To this was added 2,3-difluorobenzonitrile (2.0 g, 14.4 mmol) and the mixture stirred at 90 0C for 2 h. The mixture was partitioned between ethyl acetate and water. The organic phase was washed with water and brine then concentrated. The solid residue was triturated with 1 : 1 ethyl acetate/hexane to give the title compound as a pale brown solid (0.47 g, 13% yield). 1H-NMR (500 MHz, CDCl3) delta ppm: 7.47-7.45 (IH, m), 7.32-7.36 (2H, m), 4.08-4.02 (IH, m), 3.57 (IH, td, J- 13.0, 3,7 Hz), 3.40-3.34 (IH, m), 3.32-3.27 (IH, m), 2.44- 2.32 (2HF, m), 2.04-1.97 (2H, m), 1.90-1.84 (IH, m). LCMS [M+H]+ calcd for C11H12N2FO2S: 255.28; found: 255.13.

At the same time, in my other blogs, there are other synthetic methods of this type of compound, 21524-39-0, and friends who are interested can also refer to it.

Reference:
Patent; BRISTOL-MYERS SQUIBB COMPANY; WO2007/64316; (2007); A1;,
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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. 4640-67-9, name is 3-(4-Fluorophenyl)-3-oxopropanenitrile, This compound has unique chemical properties. The synthetic route is as follows., 4640-67-9

To a mixtureof 4-fluorobenzoylacetonitrile (100 g), methane sulfonic acid(230.6 g) and water (14 mL) was heated to 65-70 C, stirredfor 3 h and added a cyclooctanone (85 g) at same temperaturethen heated to 110 to 115 C stirred for 2 h, cool to room temperaturethen diluted with dichloromethane and water, organiclayer was separated and washed organic layer with water, thendistilled under vacuum solid obtained and purified with acetoneto get pure compound. Yield: 120 g; 73 %.

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; Sudarshan Rao; Nageswara Rao; Uma Sankara Sastry; Muralikrishna; Jayashree; Asian Journal of Chemistry; vol. 26; 18; (2014); p. 5928 – 5930;,
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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. 403-54-3, name is 3-Fluorobenzonitrile, This compound has unique chemical properties. The synthetic route is as follows., 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.

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; Rohm and Haas Company; US4063929; (1977); A;; ; Patent; Rohm and Haas Company; US4093446; (1978); A;; ; Patent; Rohm and Haas Company; US4046798; (1977); A;,
Nitrile – Wikipedia,
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105-34-0, A common heterocyclic compound, 105-34-0, name is Methyl 2-cyanoacetate, molecular formula is C4H5NO2, 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.

Benzaldehyde SI-10 (1.59 g, 15 mmol, 1.0 equiv) and methyl 2-cyanoacetate SI-6 (1.59 g, 16 mmol 1.1 equiv) were dissolved in 50 mL acetonitrile and polymer bound dimethyl benzylamine (QP-DMA, 10 g) were added. The whole mixture was stirred under N2 at 80 C for 18 h. The solvent was then removed under reduced pressure and the crude solid was recrystallised from ethanol to give 1.64 g ofwhite crystals. Isolated yield: 1.64 g (58%, 15 mmol)

The synthetic route of 105-34-0 has been constantly updated, and we look forward to future research findings.

Reference:
Article; Mallia, Carl J.; Englert, Lukas; Walter, Gary C.; Baxendale, Ian R.; Beilstein Journal of Organic Chemistry; vol. 11; (2015); p. 875 – 883;,
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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. 21524-39-0, name is 2,3-Difluorobenzonitrile, A new synthetic method of this compound is introduced below., 21524-39-0

Intermediate 52: 3-Fluoro-2-(2H-1 ,2,3-triazol-2-yl)benzoic acid.Step A: 3-Fluoro-2-(2H-1 ,2,3-triazol-2-yl)benzonitrile and 3-fluoro-2-(1 H- 1 ,2,3-triazol-1 -yl)benzonitrile. A mixture of 2,3-difluorobenzonitrile (4.0 g, 28.8 mmol), 2H-1 ,2,3-triazole (1 .9 g, 28.8 mmol) in DMF (85.0 mL) and K2C03 (7.9 g, 57.5 mmol) were heated to 125 C for 1 .5 h. After cooling to rt, water was added and the mixture extracted with EtOAc (2 X). The combined organics were washed with brine and dried (Na2S04). Purification via FCC (10-100% EtOAc in hexanes) gave two products. 3-Fluoro-2-(2H-1 ,2,3-triazol-2- yl)benzonitrile (1 .6 g, 29%), 1H NMR (CDCI3): 7.99 (s, J = 6.6 Hz, 2H), 7.67 – 7.63 (m, 1 H), 7.61 – 7.53 (m, 2H), 7.26 (s, 6 H) and 3-fluoro-2-(1 H-1 ,2,3-triazol- 1 -yl)benzonitrile (2.0 g, 38%) 1H NMR (CDCI3): 7.97 (dd, J = 4.4, 2.8 Hz, 1 H), 7.95 (d, J = 1 .2 Hz, 1 H), 7.70 (tt, J = 5.7, 2.8 Hz, 1 H), 7.65 (td, J = 8.1 , 4.9 Hz, 1 H), 7.62 – 7.57 (m, 1 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; JANSSEN PHARMACEUTICA NV; LETAVIC, Michael; RUDOLPH, Dale, A.; SAVALL, Brad, M.; SHIREMAN, Brock, T.; SWANSON, Devin; WO2012/145581; (2012); A1;,
Nitrile – Wikipedia,
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15996-76-6, Adding some certain compound to certain chemical reactions, such as: 15996-76-6, name is 4-(Aminomethyl)benzonitrile hydrochloride, 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 15996-76-6.

Synthesis of tert-butyl(4-cyanobenzyl)carbamate (7) (0149) 4-Cyanobenzylamine HCl (5.00 g, 29.7 mmol, 1.0 eq) was suspended in CH2Cl2 and NEt3 (10.3 mL, 74.1 mmol, 2.5 eq) were added to obtain a clear solution. Boc2O (8.86 mL, 38.6 mmol, 1.3 eq) was added and the solution was stirred overnight. The reaction mixture was diluted to a total volume of 100 mL with CH2Cl2 and washed with 1 M HCl (3¡Á15 mL) and sat. NaHCO3 (3¡Á15 mL). The organic layer was dried over MgSO4 and concentrated under reduced pressure. (0150) 1H NMR (500 MHz, CDCl3) delta 7.58-7.52 (m, 2H), 7.35-7.29 (m, 2H), 4.88 (s, 1H), 4.30 (d, J=6.3 Hz, 2H), 1.39 (s, 9H). (0151) 13C NMR (126 MHz, CDCl3) delta 156.2, 145.0, 132.8, 128.2, 119.1, 111.6, 80.5, 44.6, 28.8. (0152) HRMS (ESI): m/z calc. for C13H16N2NaO2+: 255.1104. found: 255.1110 (Delta=-2.0 ppm).

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 15996-76-6.

Reference:
Patent; Yale University; ERDMANN, Roman; SHRADER, Alanna Schepartz; TOOMRE, Derek; (34 pag.)US2016/115180; (2016); A1;,
Nitrile – Wikipedia,
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The chemical industry reduces the impact on the environment during synthesis 1813-33-8, name is 2-Chloro-4-(trifluoromethyl)benzonitrile, I believe this compound will play a more active role in future production and life. 1813-33-8

General procedure: A mixture of 2-chloro-4-(trifluoromethyl)-benzonitrile (1.00 mmol), appropriate boronic acid (1.20 mmol)were dissolved in toluene/dioxane:2 N Na2CO3 (2:1:1) solution(6 ml). Tetrakis(triphenyl-phosphine)palladium(0) (0.10 mmol)and 1,10-Ferrocenediyl-bis(diphenylphosphine) (0.20 mmol) wasadded to the mixture and it was refluxed for 12 h. After cooleddown to ambient temperature, the reaction was filtered over celiteand extracted with EtOAc twice. The combined organic extractswere dried over MgSO4, filtered, and concentrated in vacuo. Theresidue was purified by flash column chromatography on silicagel using EtOAc/hexanes (1:10) eluant condition. (R-B(OH)2 =1-pentenyl boronic acid for 53, 1-cyclohexenylboronicacid for 54).

The chemical industry reduces the impact on the environment during synthesis 1813-33-8. I believe this compound will play a more active role in future production and life.

Reference:
Article; Ann, Jihyae; Jung, Aeran; Kim, Mi-Yeon; Kim, Hyuk-Min; Ryu, Hyungchul; Kim, Sunjoo; Kang, Dong Wook; Hong, Sunhye; Cui, Minghua; Choi, Sun; Blumberg, Peter M.; Frank-Foltyn, Robert; Bahrenberg, Gregor; Stockhausen, Hannelore; Christoph, Thomas; Lee, Jeewoo; Bioorganic and Medicinal Chemistry; vol. 23; 21; (2015); p. 6844 – 6854;,
Nitrile – Wikipedia,
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194853-86-6, name is 4-Fluoro-2-(trifluoromethyl)benzonitrile, 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. 194853-86-6

A mixture of 4-fluoro-2- (trifluoromethyl) benzonitrile (0.158 g, 0.84 mmol), 3,3, 3- TRIFLUOROPROPYLAMINE. HCI (0.125 g, 0.84 mmol) and DIEA (0.326 g, 2.52 MMOL) in DMSO (1.5 mL) was heated under nitrogen in a microwave at 200C for 20 min. The mixture was partitioned between Et2O and 0. 1 N HCI. The organic phase was washed with 0. 1 N HCI (twice) and brine, dried (NA2SO4), and concentrated in vacuo. The residue was purified by silica gel chromatography (0-50% EtOAc-hexane gradient) and the product crystallized from ET2O-HEXANES to give the title compound as a white solid (0.144 g, 61% yield): 1H NMR (400 MHz, CDCI3) 8 7.60 (d, J = 8.6 Hz, 1 H), 6.87 (d, J = 2.4 Hz, 1 H), 6.71 (dd, J = 8.6, 2.4 Hz, 1 H), 4.56 (bs, NH), 3.53 (q, J = 6.5 Hz, 2H), 2.51-2. 40 (m, 2H); MS (ES) M/Z 283 (M+1).

Statistics shows that 194853-86-6 is playing an increasingly important role. we look forward to future research findings about 4-Fluoro-2-(trifluoromethyl)benzonitrile.

Reference:
Patent; SMITHKLINE BEECHAM CORPORATION; WO2005/795; (2005); A2;,
Nitrile – Wikipedia,
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These common heterocyclic compound, 134227-45-5, name is 3,4,5-Trifluorobenzonitrile, 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. 134227-45-5

Example 177A 3,5-difluoro-4-(4-morpholinyl)benzylamine The title compound was prepared using the procedures described in Examples 172A and 172B using 3,4,5-trifluorobenzonitrile instead of 4-fluorobenzonitrile.

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 134227-45-5.

Reference:
Patent; Lee, Chih-Hung; Bayburt, Erol K.; DiDomenico JR., Stanley; Drizin, Irene; Gomtsyan, Arthur R.; Koenig, John R.; Perner, Richard J.; Schmidt JR., Robert G.; Turner, Sean C.; White, Tammie K.; Zheng, Guo Zhu; US2004/157849; (2004); A1;,
Nitrile – Wikipedia,
Nitriles – Chemistry LibreTexts