Tag: M.W=100-200

Electric Literature of 19853-10-2, A common heterocyclic compound, 19853-10-2, name is 2-([1,1′-Biphenyl]-2-yl)acetonitrile, molecular formula is C14H11N, 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 42 Preparation of 5-cyano-5-(1,1′-biphenyl-2-yl)pentyl chloride To a stirred solution of 4.3 g. of sodium amide in 300 ml. of toluene was added dropwise over thirty minutes a solution of 19.3 g. of (1,1′-biphenyl-2-yl)acetonitrile in 200 ml. of toluene. The reaction mixture was heated at reflux for three hours, and then cooled to room temperature and stirred while a solution of 18.1 g. of 4-bromobutyl chloride in 50 ml. of toluene was added dropwise over thirty minutes. Following complete addition, the reaction mixture was heated again to reflux and stirred for sixteen hours. The reaction mixture next was cooledto room temperature and added to 500 ml. of ice water. The product was extracted from the aqueous mixture into diethyl ether. The ethereal extracts were combined and the solvent was removed by evaporation to provide the product as an oil. The oil was distilled to give 16.5 g. of 5-cyano-5-(1,1′-biphenyl-2-yl)pentyl chloride. B.P. 141-165 C. at 0.06 torr.

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; Eli Lilly and Company; US4277471; (1981); A;,
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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. 124289-21-0, name is 3-Bromo-5-methylbenzonitrile, A new synthetic method of this compound is introduced below., SDS of cas: 124289-21-0

3-Methyl-5-[(2-methyl-1,3-thiazol-4-yl)ethynyl]benzonitrile Tetrabutylammonium fluoride (3.2 mL, 1M in THF, 3.2 mmol) was added to a mixture of 3-bromo-5-methylbenzonitrile (394 mg, 2.01 mmol), 2-methyl-4-[(trimethylsilyl)ethynyl]-1,3-thiazole (605 mg, 3.10 mmol), triethylamine (0.60 mL, 4.3 mmol), copper (I) iodide (76 mg, 0.40 mmol), dichlorobis(triphenylphosphine)palladium(II) (138 mg, 0.20 mmol), and N,N-dimethylformamide (4 mL). Nitrogen was bubbled through the resulting mixture for 15 min, and the reaction was heated in a microwave reactor at 100 C. for 15 min. The solvent was removed in vacuo, and the resulting residue was chromatographed on silica gel with hexanes:EtOAc (9:1?1:1) to afford 3-methyl-5-[(2-methyl-1,3-thiazol-4-yl)ethynyl]benzonitrile as an off-white solid. 1H NMR (CDCl3, 500 MHz) delta 7.63 (s, 1H), 7.58 (s, 1H), 7.43 (s, 1H), 7.42 (s, 1H), 2.75 (s, 3H), 2.39 (s, 3H). MS (ESI) 239.5 (M++H).

The synthetic route of 124289-21-0 has been constantly updated, and we look forward to future research findings.

Reference:
Patent; MERCK & CO., INC.; US2007/60618; (2007); A1;,
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Adding a certain compound to certain chemical reactions, such as: 149793-69-1, name is 3-Fluoro-5-(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 149793-69-1, category: nitriles-buliding-blocks

To an oven-dried round bottomed flask was added nBuLi (2.5 M in hexanes, 3.6 mL, 9.0 mmol, 1.1 eq) at -45 to -40 C. under N2. An Et2O solution (12 mL) of 2-bromo-6-methoxypyridine (1 mL, 8.14 mmol) was added dropwise at the above temperature. The resulting light brownish yellow solution was stirred at -40 to -35 C. for 20 min. The mixture was cooled to -78 C., an Et2O solution (3 ml) of 3-fluoro-5-trifluoromethyl-benzonitrile (1.50 g, 7.94 mmol) was added dropwise at -78 to -70 C. The resulting solution was stirred at this temperature for 1 h. Pretreated TMSCl (1.08 mL, 8.55 mmol, 1.05 eq) was added dropwise at -78 C. The mixture was allowed to warm to room temperature for 30 min, and then stirred at room temperature for 30 min. The reaction mixture was cooled back to -78 C., and benzyl magnesium chloride (4.1 ml, 8.2 mmol) was added dropwise. The resulting mixture was stirred at -78 C. for 0.8 h, and then warmed up to room temperature for 1 h. The reaction mixture was quenched by adding sat’d NH4Cl and 1N HCl, and stirred for 10 min. The resulting solution was extracted with EtOAc, washed with 1N NaOH, saturated NaHCO3, H2O, brine, dried over MgSO4, filtered, and concentrated to dryness. The residue was purified by flash chromatography (silica gel, hexanes/EtOAc) to give 1-(3-fluoro-5-(trifluoromethyl)phenyl)-1-(6-methoxypyridin-2-yl)-2-phenylethanamine as light brownish gum (1.42 g, yield: 44.7%). LC-MS ESI (10-90% MeOH in H2O with 0.1% TFA in a 4-min run), retention time=3.20 min, 391.12 (M+H); 1H NMR (400 MHz, CDCl3) delta ppm 7.73 (s, 1H), 7.47-7.57 (m, 2H), 7.11-7.21 (m, 4H), 6.99 (d, J=7.6 Hz, 1H), 6.80 (dd, J=7.6, 2.0 Hz, 2H), 6.61 (d, J=8.1 Hz, 1H), 3.93 (s, 3H), 3.92 (d, J=13 Hz, 1H) 3.40 (d, J=13 Hz, 1H).

At the same time, in my other blogs, there are other synthetic methods of this type of compound, 3-Fluoro-5-(trifluoromethyl)benzonitrile, and friends who are interested can also refer to it.

Reference:
Patent; Bristol-Myers Squibb Company; US2007/161685; (2007); A1;,
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Reference of 869299-63-8,Some common heterocyclic compound, 869299-63-8, name is 3-Ethyl-4-fluorobenzonitrile, molecular formula is C9H8FN, 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.

Cesium carbonate (850 mg) was added to a solution of compound (5a) (200 mg) in DMSO (2.2 mL), and the mixture was heated to 130 C. The mixture was stirred for 10 minutes and 3-ethyl-4-fluorobenzonitrile (292 mg) was added thereto. The resulting mixture was stirred at the same temperature for 1.5 hours. After completion of the reaction, the reaction solution was allowed to standing still for cooling, and water was poured thereto. The reaction solution was partitioned between ethyl acetate and water. The organic layer was washed with saturated brine and dried by the addition of anhydrous sodium sulfate. After removal of the solvent by evaporation, the residue was purified by neutral silica gel column chromatography (chloroform/ethyl acetate/methanol) to obtain compound (6a) (151.8 mg, yield 54%) as a white foamy substance.

These compound has a wide range of applications. It is believed that with the continuous development of the source of the synthetic route 3-Ethyl-4-fluorobenzonitrile, its application will become more common.

Reference:
Patent; TAIHO PHARMACEUTICAL CO., LTD.; Kitade, Makoto; Ohkubo, Shuichi; Yoshimura, Chihoko; US2013/289072; (2013); A1;,
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Electric Literature of 38487-86-4,Some common heterocyclic compound, 38487-86-4, name is 2-Amino-4-chlorobenzonitrile, molecular formula is C7H5ClN2, 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 commercially available 2-amino-4-chlorobenzonitrile (1 eq., 200 mg, 1.25 mmol) , NaN3 (1.37 eq., I l l mg, 0.06 mL, 1.71 mmol) and triethylamine hydrochloride (1.37 eq., 235 mg, 1.71 mmol) were dissolved in toluene (5 mL) and stirred at 80-100C overnight. The solution was allowed to cool to room temperature and water (5 mL) was then added (three times). The aqueous phases were reunified and acidified with concentrated HC1 to give a precipitate. The precipitate was filtered off and dried to give the 5-chloro-2-(lH- l,2,3,4-tetrazol-5-yl)aniline as a brown solid (195 mg, 80%). NMR (400MHz, d6-DMSO): 7.72 (d, 1H, J = 8.4 Hz), 6.96 (d, 1H, J = 2 Hz), 6.73 (dd, 1H, J = 8.4 -2 Hz) 13C NMR (100MHz, d6-DMSO): 148.52, 136.24, 129.73, 115.34, 115.09

The synthetic route of 38487-86-4 has been constantly updated, and we look forward to future research findings.

Reference:
Patent; INSERM (INSTITUT NATIONAL DE LA SANTE ET DE LA RECHERCHE MEDICALE); UNIVERSITE DE MONTPELLIER; CENTRE NATIONAL DE LA RECHERCHE SCIENTIFIQUE (CNRS); UNIVERSITE DE STRASBOURG; VALMIER, Jean; LEYRIS, Jean-Philippe; ROGNAN, Didier; SCHMITT, Martine; (80 pag.)WO2016/16370; (2016); A1;,
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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. 868-54-2, name is 2-Aminoprop-1-ene-1,1,3-tricarbonitrile, A new synthetic method of this compound is introduced below., Application In Synthesis of 2-Aminoprop-1-ene-1,1,3-tricarbonitrile

General procedure: mmol), malononitrile dimer (1.5 mmol), AcOH (1 mmol), piperidine(1 mmol), and EtOH (10 mL) were stirred at refluxing for1 h. After completion of the reaction (confirmed by TLC), thereaction mixture was filtered to afford the crude product, whichwas further washed with 95% EtOH to give pure product 4. Thestructures of the products were well characterized by NMR andHRMS studies. The characterization data of representative compound 4a. Compound 4a: light yellow solid; mp 300.9-302.0 C. 1H NMR(400 MHz, DMSO-d6): delta = 9.33 (s, 1 H), 7.37 (d, J = 7.6 Hz, 2 H),7.25 (d, J = 7.6 Hz, 2 H), 6.41 (s, 2 H), 6.24 (s, 2 H), 5.40 (s, 1 H),4.08 (t, 2 H), 3.89-3.73 (m, 2 H) ppm. 13C NMR (100 MHz,DMSO-d6): delta = 159.8, 154.2, 152.4, 149.1, 142.5, 130.9, 129.7,127.6, 116.6, 106.6, 92.6, 69.9, 44.4, 43.3, 36.6 ppm. ESI-HRMS:m/z calcd for C17H1435ClN7O2 [M – H]-: 382.0898; found:382.0811; calcd for C17H1437ClN7O2 [M – H]-: 384.0898; found:384.0771

The synthetic route of 868-54-2 has been constantly updated, and we look forward to future research findings.

Reference:
Article; Sun, Feilong; Zhu, Fengjuan; Shao, Xusheng; Li, Zhong; Synlett; vol. 26; 16; (2015); p. 2306 – 2312;,
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Synthetic Route of 4513-77-3, These common heterocyclic compound, 4513-77-3, name is 2-Oxocyclohexanecarbonitrile, 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 triphenylphosphine (29.9 g, 114 mmol) in 500 ml_ of THF, cooled to 0 0C, was slowly added a 40% solution of diethyl azodicarboxylate in toluene (52.2 ml_, 114 mmol), ethyl glycolate (10.8 ml_, 114 mmol) and 2- oxocyclohexanecarbonitrile (10 g, 81.3 mmol). The resulting solution was stirred at room temperature for 20 hours. Then 50% sodium hydride (11 g, 229 mmol) was added and the mixture was stirred at room temperature for 5 hours. The reaction mixture was cooled to 0 0C and a pH 7.8 phosphate buffer (Na2HPO4/KH2PO4) solution (375 ml_) was added. THF was evaporated and the resulting aqueous solution was extracted with EtOAc. The organic phase was dried over Na2SO4 and concentrated to dryness. The resulting crude product was chromatographed on silica gel using hexane/EtOAc mixtures of increasing polarity as eluent, to afford 8.5 g of the desired compound (yield: 50%). LC-MS (Method 2): tR = 1.97 min; m/z = 210 (MH+).

Statistics shows that 2-Oxocyclohexanecarbonitrile is playing an increasingly important role. we look forward to future research findings about 4513-77-3.

Reference:
Patent; PALAU PHARMA, S. A.; WO2009/56551; (2009); A1;,
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Electric Literature of 4513-77-3, 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. 4513-77-3, name is 2-Oxocyclohexanecarbonitrile belongs to nitriles-buliding-blocks compound, it is a common compound, a new synthetic route is introduced below.

To a solution of 2-oxocyclohexanecarbonitrile (250 mg, 2.03 mmol) in EtOH (20 mL) was added CHCI3 (1 mL) and Pt02 (55.3 mg, 0.244 mmol) and the reaction mixture was stirred under hydrogen atmosphere (3 atm) for 67 h. Subsequently the reaction mixture was filtered over Celite and 4N HCI in dioxane was added to the filtrate, which was then concentrated to afford the title compound. The product was used in the next step without further purification.

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

Reference:
Patent; NOVARTIS AG; ALTMANN, Eva; HOMMEL, Ulrich; LORTHIOIS, Edwige, Liliane, Jeanne; MAIBAUM, Juergen, Klaus; OSTERMANN, Nils; QUANCARD, Jean; RANDL, Stefan, Andreas; VULPETTI, Anna; WO2014/2054; (2014); A1;,
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Electric Literature of 268734-34-5, 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 268734-34-5 as follows.

To a solution of ethanehydroxamic acid (0.629 g, 8.37 mmol) in DMF (5 ml.) was added potassium 2-methylpropan-2-olate (0.94 g, 8.4 mmol) and the reaction was stirred for 30 minutes. Methyl 4-cyano-3-fluorobenzoate (1.0 g, 5.6 mmol) was added followed by DMF (2 ml.) and the reaction was stirred for a further 2 hours at room temperature. The reaction was diluted with ethyl acetate (50 ml.) and water (50 ml_), the aqueous layer was extracted with ethyl acetate and the combined organic layers were washed with water, dried, filtered and concentrated. The crude material was purified by silica gel chromatography (12 g Si02 cartridge, 0-50% EtOAc in petroleum benzine 40-60 C) to give the title compound (0.55 g, 51% yield) as a white solid. 1H NMR (400 MHz, CDCIs) d 8.12 (d, J = 1.02 Hz, 1H), 7.96 (dd, J = 1.24, 8.29 Hz, 1H), 7.59 (dd, J = 0.77, 8.25 Hz, 1H), 3.98 (s, 3H). LCMS: rt 2.97 min, m/z 193.0 [M+H]+.

According to the analysis of related databases, 268734-34-5, the application of this compound in the production field has become more and more popular.

Reference:
Patent; CTXT PTY LIMITED; STUPPLE, Paul, Anthony; LAGIAKOS, Helen, Rachel; MORROW, Benjamin, Joseph; FOITZIK, Richard, Charles; HEMLEY, Catherine, Fae; CAMERINO, Michelle, Ang; BOZIKIS, Ylva, Elisabet, Bergman; WALKER, Scott, Raymond; (321 pag.)WO2019/243491; (2019); A1;,
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Some common heterocyclic compound, 939-80-0, name is 4-Chloro-3-nitrobenzonitrile, molecular formula is C7H3ClN2O2, 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. Application In Synthesis of 4-Chloro-3-nitrobenzonitrile

In dry acetonitrile (40 ml) were dissolved 4-chloro-3-nitrobenzonitrile (4.0 g, 21 .98 mmol), ethyl glycinate hydrochloride (4.6 g, 32.97 mmol) and diisopropyl ethylamine (10.9 ml, 65.94 mmol) in microwave vial and the mixture was irradiated at 125 C for 30 minutes. The solvent was removed under reduced pressure. The obtained residue was purified by silica gel column chromatography (ethyl acetate/hexane) to yield 4.0g (73.13%) of the title compound . 1 H- NMR(400MHz,CDCl3)delta: 1.33(t,J=7.2Hz,3H),4.13(d,J=5.2Hz,2H),4.32(q,J=7.2Hz,2H ),6.77 Eta),8.81 (5, 1 H).

These compound has a wide range of applications. It is believed that with the continuous development of the source of the synthetic route 939-80-0, its application will become more common.

Reference:
Patent; DAIICHI SANKYO COMPANY, LIMITED; KATOCH, Rita; INAGAKI, Hiroaki; FUJISAWA, Tetsunori; WO2014/24056; (2014); A1;,
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