Nitriles-buliding-blocks

A common compound: 4640-67-9, name is 3-(4-Fluorophenyl)-3-oxopropanenitrile, belongs to nitriles-buliding-blocks compound, it can change the direction of chemical reaction, and react with certain compounds to generate new functional products. A new synthetic method of this compound is introduced below. 4640-67-9

In a 25 mL reaction tube with a Teflon magnetic stir bar,Add 0.5 mmol of 4-fluorobenzoylacetonitrile, 0.5 mmol of 3-bromo-1,1,1-trifluoroacetone, 0.5 mmol of sodium acetate,Finally, 58 mmol of 1,4-dioxane was added, and the reaction was stirred at room temperature for 8 hours.Add 15 mL of water, extract three times with 10 mL of ether, and combine the organic phases.Washing with saturated sodium chloride solution, drying over anhydrous magnesium sulfate, and then removing the organic solvent by rotary evaporation;The obtained crude product was eluted with n-pentane and ethyl acetate (10:1, v/v).2-(4-Fluorophenyl)-5-hydroxy-5-(trifluoromethyl)-4,5-dihydrofuran-3-carbonitrile was isolated by silica gel column chromatography (yield: 76%).

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, 4640-67-9, other downstream synthetic routes, hurry up and to see.

Reference:
Patent; Fuzhou University; Weng Zhiqiang; Wang Junwen; (29 pag.)CN110272400; (2019); A;,
Nitrile – Wikipedia,
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79463-77-7,Some common heterocyclic compound, 79463-77-7, name is Diphenyl N-cyanocarbonimidate, molecular formula is C14H10N2O2, 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 solution of (R)-3-tert-butoxycarbonylaminopipiridine (154.0 g, 0.769 mol) in iPrOH (3.0 L) was added diphenyl cyanocarbonimidate (183.2 g, 0.769 mol). The mixture was stirred at room temperature for 2.5 h. To the reaction mixture was added glycine ethyl ester¡¤hydrochloride (536.7 g, 3.85 mol) at 0 C, and the mixture was stirred at 80 C for 6 h. After cooling to room temperature, the reaction mixture was diluted with AcOEt (1.4 L) and the precipitate was removed by filtration through a Celite pad. The filtrate was concentrated in vacuo, and the residue was diluted with 5% sodium carbonate solution and extracted with CHCl3 three times. The combined organic layers were dried over Na2SO4, and concentrated in vacuo. The residue was purified by silica-gel column chromatography to give 7 (249.2 g, yield 92%) as a pale yellow oil. 1H NMR (300 MHz, CDCl3) delta 5.68 (br s, 1H), 4.66 (br s, 1H), 4.28-4.19 (m, 4H), 3.81-3.34 (m, 5H), 2.05-1.51 (m, 4H), 1.45 (s, 9H), 1.30 (t, J=7.2 Hz, 3H); 13C NMR (75 MHz, CDCl3) delta 169.6, 160.0, 155.5, 117.1, 80.1, 61.8, 51.2, 47.3, 45.4, 44.6, 29.8, 28.3, 22.8, 14.1; HRMS (ESI) [M+H]+ calcd for C16H28N5O4 354.2136, found 354.2128; IR (ATR): 1743, 1685, 1575, 1531, 1440, 1390, 1365, 1309, 1243, 1197, 1162, 1051, 1031, 1018 cm-1.

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

Reference:
Article; Ikuma, Yohei; Nakahira, Hiroyuki; Tetrahedron; vol. 67; 49; (2011); p. 9509 – 9517;,
Nitrile – Wikipedia,
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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 218632-01-0 as follows. 218632-01-0

Compound 161a: 3-Fluoro-4-nitro-benzamide: The urea/hydrogen peroxide complex (22.65 g, 240.8 mmol, 2.0 eq) was added to a solution of 3-fluoro-4-nitro-benzonitrile (20.0 g, 120.4 mmol, 1.0 eq) and potassium carbonate (33.28 g, 240.8 mmol, 2.0 eq) in 20% water/acetone (500 ml). The reaction was stirred at room temperature for 22 hours when urea/hydrogen peroxide complex (11.33 g, 120.4 mmol, 1.0 eq) and potassium carbonate (16.64 g, 120.4 mmol, 1.0 eq) were added. The reaction was stirred for a further 2 hours at room temperature then diluted with water (300 ml) and DCM (500 ml). The organic layer was removed and the aqueous extracted with DCM (2 x 500 ml). The organics were combined, washed with brine, dried over sodium sulphate, and the solvent removed in vacuo to give the title compound as an orange solid (14.065 g, 76.31 mmol, 63%). 1H NMR shows product in >95% purity.

According to the analysis of related databases, 218632-01-0, the application of this compound in the production field has become more and more popular.

Reference:
Patent; DEVELOGEN AKTIENGESELLSCHAFT; WO2006/136402; (2006); A1;,
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A common heterocyclic compound, 1953-99-7, name is 3,4,5,6-Tetrachlorobenzene-1,2-dicarbonitrile, 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. 1953-99-7.

[formula c] 0.0375 mol, [formula a]0.0125 mol, zinc bromide 0.015 mol and1,8- diazabicyclo [5.4.0] undec -7-ene 0.05 mol were added to amylalcohol 66 g and stirred. The reaction temperature was raised to 130 and the reaction was carried out for 8 hours. After thereaction was complete, the reaction solution was cooled down and concentratedunder reduced pressure to remove the solvent by 2/3. The addition of methanolwas followed by to crystalize the solution. The crystals were filtered underreduce pressure and was dispersedly filtered in the mixed solution of methanol50g for 1 hour. The crystals were suction filtered and vacuum dried at 60 to obtain phthalocyanine compound 7.9g.

The synthetic route of 3,4,5,6-Tetrachlorobenzene-1,2-dicarbonitrile has been constantly updated, and we look forward to future research findings.

Reference:
Patent; Kyung-In Synthetic Corporation; Park, Soon Hyeon; Kim, Jeong Ki; Kim, Jeong Rok; Lee, Yun Ah; Lee, Do kyeong; Lee, Min Jeong; Lee, Hui Jae; (16 pag.)KR2016/7024; (2016); A;,
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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 19179-31-8 as follows. 19179-31-8

Step 2: 3,5-dihydroxybenzonitrile To a solution of 3,5-dimethoxybenzonitrile (2 g, 2.2 mmol) in dichloromethane (20 mL) was added slowly BBr3 (15 mL, 1 M, 15 mmol) at -50 C. under N2. After addition, the mixture was stirred at -50 C. for 2 h and stirred at r.t for 20 hr. The mixture was slowly poured into ice-water with stirring and extracted with dichloromethane. The organic layer was washed with brine, dried over sodium sulfate, filtered and concentrated under reduced pressure. The residue was purified by column (petroleum ether/ethyl acetate (2:1) as eluent) to afford 3,5-dihydroxybenzonitrile (1.43 g). 1H NMR (DMSO-d6, 400 MHz): delta 10.02 (s, 2H), 6.56 (d, J=2.0 Hz, 2H), 6.51 (t, J=2.0 Hz, 1H).

According to the analysis of related databases, 19179-31-8, the application of this compound in the production field has become more and more popular.

Reference:
Patent; Arrington, Kenneth L.; Burgey, Christopher; Gilfillan, Robert; Han, Yongxin; Patel, Mehul; Li, Chun Sing; Li, Yaozong; Luo, Yunfu; Lei, Zhiyu; US2014/100231; (2014); A1;,
Nitrile – Wikipedia,
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6136-68-1, 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. 6136-68-1 name is 3-Acetylbenzonitrile, 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.

A solution of n-BuLi (20.0 mL, 2.5 M, 50.0 mmol) was added to a solution of PPh3MeI (20.2 g, 50.0 mmol) in THF (200 mL) at -10 C. After the mixture was stirred at -10 C for 1 h, 3-acetylbenzonitrile (4.85 g, 33.4 mmol) was added. The mixture was allowed to warm up to r.t. and stirred at r.t. for 3 h. Water (400 mL) was added to the reaction mixture and it was extracted with CH2Cl2 (200 mL x 2). It was dried over anhydrous sodium sulfate, and purified by column chromatography (PE: EtOAc = 50: 1) to give the titled compound (3.4 g, 79%).

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

Reference:
Patent; F. HOFFMANN-LA ROCHE AG; BURCH, Jason; GOLDSMITH, Richard, A.; ORTWINE, Daniel, Fred; PASTOR, Richard; PEI, Zhonghua; WO2013/24011; (2013); A1;,
Nitrile – Wikipedia,
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13388-75-5, Adding some certain compound to certain chemical reactions, such as: 13388-75-5, name is 2-(3,5-Dimethoxyphenyl)acetonitrile, 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 13388-75-5.

Under a nitrogen atmosphere, add 0.2 mmol of 3,5-dimethoxyphenylacetonitrile to a 25 mL reaction flask equipped with a reflux condenser.0.6 mmol of lithium tert-butoxide, 0.6 mmol of alpha-trifluoromethylstyrene, 4 ml of dimethyl sulfoxide, the reaction system was stirred at 80C for 12 hours,Stop heating and stirring, cool to room temperature, add water to quench the reaction, add ethyl acetate to extract the reaction solution,The ethyl acetate layer was subjected to rotary evaporation under reduced pressure to remove the solvent, and then separated and purified by column chromatography to obtain the target product,The column chromatography eluent used was a petroleum ether: ethyl acetate mixed solvent with a volume ratio of 30:1; the yield of the product was 83%.

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 13388-75-5.

Reference:
Patent; South China University of Technology; Zhu Chuanle; Cai Yingying; Zeng Hao; Jiang Huanfeng; (21 pag.)CN111205202; (2020); A;,
Nitrile – Wikipedia,
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95-11-4, Adding a certain compound to certain chemical reactions, such as: 95-11-4, name is 5-Norbornene-2-carbonitrile, 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 95-11-4.

Example 1; Into a 50-ml glass round bottom flask equipped with a stirrer, a thermometer, a nitrogen inlet tube and a condenser were introduced 1.07 g (4.5 mmol) of nickel chloride hexahydrate, 0.60 g (9.2 mmol) of zinc, 8.90 g (28.7 mmol) of TPP containing 0.2 weight % of triphenyl phosphate purified by a known method and 26. 5 g (22.2 mmol) of CNN, and the replacement with nitrogen was surely carried out for the gas phase to obtain a tetrakis(triphenyl phosphite) nickel catalyst. Next, into a 1-L glass flat bottom separable flask equipped with a stirrer, a thermometer, a nitrogen inlet tube, a hydrogen cyanide inlet tube and a condenser were introduced 307.0 g (2.58 mol) of CNN, 90.0 g of toluene and the catalyst synthesis solution obtained as above, and the replacement with nitrogen was fully carried out for the gas phase at room temperature and then the temperature was elevated to 60 degrees centigrade. Then, 69.13 g (2.66 mol) of liquid hydrogen cyanide was supplied over 3.5 hours and hydrogen cyanide reaction was carried out to obtain 480.7 g of a coarse DCN. Nitrogen gas was bubbled in 480.7 g of the resulting coarse DCN at a flow rate of 500 ml/min for 1 hour for degassing, and then insoluble substances were filtered off. To this filtrate was added 1.9 g of 40% sulfuric acid, and the resulting solution was heated at 60 degrees centigrade for 3 hours for carrying out acid decomposition of the catalyst. 5.5 g of 25 weight % sodium hydroxide was further added thereto and the mixture was heated at 40 degrees centigrade for 2 hours and neutralized, and then 449.0 g of toluene was added for extracting DCN to obtain a DCN toluene solution. Then, toluene was removed to obtain 447.6 g of 85 weight % DCN. The resulting DCN was analyzed and as a result, triphenyl phosphate was not contained therein. Next, into a 500-ml autoclave were introduced 287.8 g of DCN obtained above, 32.6 g of 25% ammonia water and 7.9 g of a Raney cobalt catalyst, and the catalytic hydrogenation reaction was carried out at 120 degrees centigrade at hydrogen pressure of 3.5 MPa for 430 minutes. The resulting solution was cooled to room temperature and filtered to remove the Raney cobalt catalyst, and then 0.5 g of 32 weight % caustic soda was added to the filtrate for removing ammonia and toluene contained in DCN at 75 degrees centigrade at 2.6 KPa. Subsequently, the resulting residue was distilled under conditions of 0.1 MPa and a temperature in the flask of 150 to 160 degrees centigrade to obtain 204 g of NBDA. Phenol was analyzed and as a result, NBDA did not contain phenol. Furthermore, the obtained NBDA was sealed with nitrogen and then tightly closed up. The resultant was stored in a light-shielded vessel at room temperature (25 to 35 degrees centigrade) for 1 month and then time-dependent coloring was confirmed and as a result, no time-dependent coloring was found as APHA was not more than 10. The test results are shown in Table 1.; Example 2; The test was conducted in the same manner as in Example 1 using TPP containing 0.6 weight % of triphenyl phosphate. Said TPP was purified by a known method. The resulting DCN was analyzed and as a result, 0.08 weight % of triphenyl phosphate was contained therein. NBDA obtained by using this DCN contained 0.04 weight % of phenol. However, it was stored in a light-shielded vessel at room temperature (25 to 35 degrees centigrade) for 1 month and then time-dependent coloring was confirmed and as a result, no time-dependent coloring was found as APHA was not more than 10. The test results are shown in Table 1.; Comparative Example 1; The test was conducted in the same manner as in Example 1 using TPP containing 1.1 weight % of triphenyl phosphate. The resulting DCN was analyzed and as a result, 0.25 weight % of triphenyl phosphate was contained therein. NBDA obtained by using this DCN contained 0.20 weight % of phenol. It was stored in a light-shielded vessel at room temperature (25 to 35 degrees centigrade) for 1 month and then time-dependent coloring was confirmed and as a result, time-dependent coloring was confirmed as APHA was 30. The test results are shown in Table 1.

According to the analysis of related databases, 95-11-4, the application of this compound in the production field has become more and more popular.

Reference:
Patent; Mitsui Chemicals, Inc.; EP2036883; (2009); A1;,
Nitrile – Wikipedia,
Nitriles – Chemistry LibreTexts

35704-19-9, Adding a certain compound to certain chemical reactions, such as: 35704-19-9, name is N-(4-Cyanophenyl)acetamide, 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 35704-19-9.

PREPARATION 9 An aqueous solution (200 ml) of calcium hypochlorite (21 g) was added to a solution of p-cyanoacetanilide (12.5 g) in ethanol (27 ml), acetic acid (27 ml), and water (27 ml). The mixture was stirred for 4 days and extracted with chloroform. The organic layer was washed with a saturated aqueous solution of sodium chloride, dried over magnesium sulfate, and concentrated to give a powder of 2′-chloro-4′-cyanoacetanilide (12.5 g).

According to the analysis of related databases, 35704-19-9, the application of this compound in the production field has become more and more popular.

Reference:
Patent; Fujisawa Pharmaceutical Co., Ltd.; US4866091; (1989); A;,
Nitrile – Wikipedia,
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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 123-06-8 as follows. 123-06-8

To a solution of ethoxymethylenemalonodinitrile (S) (80 mmol) in benzene is added hydrazine (150 mmol). The reaction is stirred at reflux for 1 hr, diluted into ethyl acetate, washed with sodium bicarbonate solution and concentrated under vacuum, to provide T.

According to the analysis of related databases, 123-06-8, the application of this compound in the production field has become more and more popular.

Reference:
Patent; CONCERT PHARMACEUTICALS INC.; WO2008/5471; (2008); A2;,
Nitrile – Wikipedia,
Nitriles – Chemistry LibreTexts