Month: November 2020

2032-34-0, A common compound: 2032-34-0, name is 3,3-Diethoxypropanenitrile, 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.

Example 4 Methyl 2-[(2-cyanovinyl)amino]-4-ethoxy-5-acetylamidobenzoate (a compound of formula I, R=methyl) Trifluoroacetic acid (70 mL) was mixed with water (11 mL, 0.6 mol) at room temperature, and 2-cyanoacetaldehyde diethylacetal (23 mL, 0.15 mol, commercially available) was added thereto. The mixture was reacted for 12 h at room temperature to obtain a solution 1. In addition, the title compound of example 3 (a compound of formula II, i.e. methyl 4-ethoxy-5-acetylamido-2-aminobenzoate) (30 g, 0.12 mol) was suspended in ethyl acetate (400 mL), and the above obtained solution 1 was added thereto. The reaction mixture first turned to clear and then changed to cloudy. After reacted for 3-5 h at room temperature, the reaction was finished. The reaction mixture was filtered, washed with ethyl acetate and dried to give 35 g of the title compound as an offwhite powder with a yield of 96%. 1HNMR (300 MHz, DMSO) delta 1.39 (t, 3H), 2.06 (s, 3H), 3.82 (s, 3H), 4.25 (q, 2H), 5.14 (d, 1H), 7.05 (s, 1H), 8.21 (t, 1H), 8.41 (s, 1H), 9.02 (s, 1H), 10.41 (d, 1H). MS/ESI: 303.9 (M+H), 326.0 (M+Na), 302.0 (M-H).

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, 3,3-Diethoxypropanenitrile, other downstream synthetic routes, hurry up and to see.

Reference:
Patent; Shanghai Institute of Materia Medica, Chinese Academy of Sciences; Topharman Shangai Co., Ltd.; US2011/263860; (2011); A1;,
Nitrile – Wikipedia,
Nitriles – Chemistry LibreTexts

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.

Potassium tert-butoxide (4.5 g, 40.10mmol) was taken in dry diethyl ether (200ml)at room temperature under N2 atmosphere at stirring condition. Diethyl oxalate (4.4 ml, 30.10mmol) was added to that solution. After 15 min of stirring, 3-acetylbenzonitrile (4.35 g, 29.96 mmol) was added to the resulting mixtureand the stirring was continuing for overnight.A light yellow precipitate was obtained and the whole resulting mixture is taken in a separating funnel. This solution was washed three times with 20 ml of water. The entire aqueous layer was collected in a beaker, cooled for some time and then dilute HCl (2 ml) was added to it dropwise until the whole solution became just acidic. A yellow precipitate was obtained which was filtered and product ethyl 4-(3-cyanophenyl)-2,4-dioxobutanoatewas isolated as a yellow solid (3.3 g, 76.74 yield).

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:
Article; Roy, Manasi; Adhikary, Amit; Debnath, Tanay; Das, Abhijit Kumar; Mondal, Raju; Polyhedron; vol. 160; (2019); p. 46 – 52;,
Nitrile – Wikipedia,
Nitriles – Chemistry LibreTexts

A common heterocyclic compound, 6011-14-9, name is 2-Aminoacetonitrile hydrochloride, molecular formula is C2H5ClN2, 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. 6011-14-9.

General procedure: The aminoacetonitrile hydrochloride was added to a solution of xylene in triethylamine,Heated to 40 for 15 min,Preparation of amino acetonitrile solution;4-trifluoromethylnicotinic acid was dissolved in xylene,Added to the above amino acetonitrile solution,Cooling to -10 C, slowly dropping oxalyl chloride in xylene solution,To be added dropwise,Heated to 45 reaction 1h,Then continue to raise the temperature to 100 reaction 2 h;among them,Aminoacetonitrile hydrochloride and triethylamine in a molar ratio of 1: 2.5; 4-trifluoromethylnicotinic acid and aminoacetonitrile hydrochlorideReaction molar ratio of 1: 0.5; 4-trifluoromethyl nicotinic acid and oxalyl chloride reaction molar ratio of 1: 1.05.After the reaction was completed, the temperature was lowered to 85 C and hot filtration was performed to obtain a filtrate 1 and an organic salt. The resulting filtrate1 slowly cooled to room temperature, transferred to a cryogenic tank, -5 crystallization, filtration,The filtrate 2 (in which N-cyanomethylbis (trifluoromethyl) nicotinamide, flonicamid, 4-trifluoromethylnicotinic acid, xylene and triethylamine was included in the filtrate 2)The filter cake is washed with water,And the volume ratio of 82:18 methyl tert-butyl ether and ethyl acetate solution was recrystallized,A white N-cyanomethylbis (trifluoromethyl) nicotinamide solid powder was obtained,The yield was 71.1% and the purity after purification was 99.9%. Examples 2-5 are respectively a preparation method of N-cyanomethylbis (trifluoromethyl) nicotinamide and N-cyanomethylbisMethyl) nicotinamide, which is similar to the preparation method and application described in Example 1, except that the amount of raw materials involved, the technical parameters involved in the preparation method and the application are different, as follows Table shows:

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

Reference:
Patent; Hebei University of Science and Technology; Dong Xinrui; Shu Xueye; Wang Yingnan; Guo Qingchun; Zhang Yue; (17 pag.)CN107286086; (2017); A;,
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. 874-89-5, name is 4-(Hydroxymethyl)benzonitrile, A new synthetic method of this compound is introduced below., 874-89-5

EXAMPLE 6 4-({[4-(2,4-Diamino-6-ethylpyrimidin-5-yl)phenyl]amino}methyl)benzonitrile Synthesis was performed using a PE Biosystems (Applied Biosystems) Solaris 530 organic synthesizer. 4-Cyanobenzyl alcohol (0.6 mmol) was dissolved in 3 mL DMA then transferred to a 4 mL vial containing 0.5 mmol of Dess-Martin Reagent. The vial was shaken to ensure mixing then used directly. A round bottom flask was charged with 3 equivalents of MP-BH3CN. The block was placed on the Solaris 530 and 1 equivalent of 5-(4-amino-phenyl)-6-ethyl-pyrimidine-2,4-diamine from Example 1C (dissolved in 1:1 MeOH/CH2Cl2) was added to the round bottom flask. The oxidized 4-cyanobenzyl alcohol was then added (2 eq) followed by 3 equivalents of a solution of HOAc in 1:1 MeOH/CH2Cl2. The block was then heated to 55C overnight. The mixture was transferred with MeOH to a 20 mL vial containing scavenger resins PS-TsNHNH2 and MP-Carbonate (3 eq each). The resins were filtered and the product concentrated. Purification by Reverse Phase HPLC to provided the titled compound. 1H NMR (500 MHz, DMSO-d6) delta ppm 0.94 (t, J=7.49 Hz, 3 H), 2.11 (q, J=7.59 Hz, 2 H), 4.38 (d, J=5.93 Hz, 2 H), 5.32 (s, 2 H), 5.77 (s, 2 H), 6.44 (t, J=5.93 Hz, 1 H), 6.61 (d, J=8.42 Hz, 2 H), 6.85 (d, J=8.42 Hz, 2 H), 7.58 (d, J=8.11 Hz, 2 H), 7.80 (d, J=8.11 Hz, 2 H); MS (ESI) positive ion 345(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; Kosogof, Christi; Liu, Bo; Liu, Gang; Liu, Mei; Nelson, Lissa T.J.; Serby, Michael D.; Sham, Hing L.; Szczepankiewicz, Bruce G.; Xin, Zhili; Zhao, Hongyu; US2005/70712; (2005); A1;,
Nitrile – Wikipedia,
Nitriles – Chemistry LibreTexts

60758-86-3, Adding some certain compound to certain chemical reactions, such as: 60758-86-3, name is 3-Ethoxy-4-methoxybenzonitrile, 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 60758-86-3.

Dimethyl sulfone (53.1 g, 564 mmoles) was added to mixture of tetrahydrofuran (1000 ml) and dimethylsulfoxide (50 ml) and stirred at room temperature for 5-10 minutes. Sodium amide (22.02 g, 564 mmoles) was added slowly to the reaction mixture at 40C and stirred for 10-15 minutes. 3-ethoxy-4-methoxy benzonitrile (50 g, 282 mmoles) in tetrahydrofuran (200 ml) was added to the reaction mixture over a period of 30 minutes and was stirred for three hours at room temperature. The reaction mixture was distilled under reduced pressure at 40-45 C. Water (750m1) was added to the reaction mass and stirred at 35-40C for 30 minutes. The solid was filtered, washed with water (150 ml) and dried under reduced pressure at 45-50 C to give the title compound.Yield: 63.7 g (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 60758-86-3.

Reference:
Patent; DR. REDDY?S LABORATORIES LIMITED; VAKAMUDI, Sree Naga Venkata Lakshmi Vara Prasad; KUNHIMON, Syam Kumar Unniaran; SARKAR, Soma Rani; IRENI, Babu; LEKKALA, Amarnath Reddy; RAPAKA, Gangadhara Chary; MADARAPU, Srinivasa Rao; NADGOUD, Ramesh Kumar; CHAGANTI, Sridhar; MUVVA, Venkateswarlu; FRYSZKOWSKA, Anna; FOX, Martin; SOLARES, Tamara Fanjul; SHANGAPU, Vijay Kumar; HASTAK, Nilesh; VYALA, Sunitha; RANGINENI, Srininvasulu; (49 pag.)WO2016/199031; (2016); A1;,
Nitrile – Wikipedia,
Nitriles – Chemistry LibreTexts

Adding a certain compound to certain chemical reactions, such as: 555-21-5, name is 4-Nitrophenylacetonitrile, 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 555-21-5, 555-21-5

VI 5-0 g (30 mmol) was taken,Dissolved in 25 ml of ethanol,8 g (150 mmol) NH4Cl,Dissolved in 40 ml of water,Was added to a three-necked flask,5. 05 g (90 mmol) of iron powder was added,Mechanical stirring,Reflux 2h.Filter in addition to iron powder,CH2CV washing filter cake,Extraction with CH2C12,Saturated sodium chloride,Dried over anhydrous sodium sulfate,filter,Evaporated to dryness 3. 86 g of solid,The yield was 97.5%

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

Reference:
Patent; Hefei Industrial Pharmaceutical Institute Co., Ltd.; China Pharmaceutical University; NANJING MEDICAL INDUSTRY MEDICAL TECHNOLOGY CO LTD;; Xu, Yungen; Liu, Wei; He, Guangwei; Yang, Yun; Bian, Xueguo; (9 pag.)CN103408501; (2016); B;,
Nitrile – Wikipedia,
Nitriles – Chemistry LibreTexts

A common compound: 179898-34-1, name is 3-Bromo-5-fluorobenzonitrile, 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. 179898-34-1

(i) 3-bromo-5-methoxybenzonitrile Sodium methoxide (2.02 g) was added to a stirred solution of 3-fluoro-5-bromobenzonitile (5.0 g) in DMPU (20 ml) and stirred at RT for 2 h. The reaction was diluted with water and the resulting solid formed was filtered and washed with water, then dried in vacuo to give the subtitle compound (5.10 g). 1H NMR DMSO-d6: 7.39-7.38 (1H, s), 7.30-7.26 (1H, m), 7.11 (1H, s), 3.83 (3H, s).

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, 179898-34-1, other downstream synthetic routes, hurry up and to see.

Reference:
Patent; ASTRAZENECA AB; US2008/293775; (2008); A1;,
Nitrile – Wikipedia,
Nitriles – Chemistry LibreTexts

6136-68-1,Some common heterocyclic compound, 6136-68-1, name is 3-Acetylbenzonitrile, molecular formula is C9H7NO, 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 34A Ethyl 4-(3-cyanophenyl)-1,3-thiazole-2-carboxylate At room temperature, 10 drops of a conc. aqueous hydrogen chloride solution are added to 5.00 g (34.4 mmol) of 3-acetylbenzenecarbonitrile in 40 ml of conc. acetic acid. 1.8 ml (34.4 mmol) of bromine in 10 ml of conc. acetic acid are subsequently added dropwise over a period of 1 h, and after the end of the addition, the reaction mixture is poured onto ice. After extraction of the aqueous phase with dichloromethane, the combined organic phases are dried over MgSO4, filtered and concentrated under reduced pressure. The solid obtained (8.00 g) is provided in 250 ml of EtOH and heated under reflux, a solution of 3.77 g (28.3 mmol) of ethyl amino(thioxo)acetate in 50 ml of ethanol is added dropwise and the mixture is stirred under reflux for 3 h. The reaction solution is cooled and the precipitate formed is collected by filtration. The mother liquor is concentrated under reduced pressure, the residue is taken up in a little ethanol and the solid formed is subsequently collected by filtration. 5.75 g (65% of theory) of the title compound are obtained after combining the solids. 1H-NMR (400 MHz, DMSO-d6): delta=8.74 (s, 1H), 8.45 (s, 1H), 8.35 (d, 1H), 7.88 (d, 1H), 7.77-7.62 (m, 1H), 4.43 (q, 2H), 1.37 (t, 3H). LC-MS (Method 5): Rt=1.15 min; MS (ESIpos): m/z=259 [M+H]+.

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

Reference:
Patent; AiCuris GmbH & Co. KG; Thede, Kai; Greschat, Susanne; Gericke, Kersten Matthias; Wildum, Steffen; Paulsen, Daniela; US2013/45999; (2013); A1;,
Nitrile – Wikipedia,
Nitriles – Chemistry LibreTexts

1080-74-6, Name is 2-(3-Oxo-2,3-dihydro-1H-inden-1-ylidene)malononitrile, 1080-74-6, 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.

As shown in the above reaction formula,The formula (2-8-a-3) obtained in the above Preparation Example 1The compound shown (129 mg, 0.1 mmol),a compound of the formula (a-2-1) (92 mg, 0.4 mmol),Pyridine (0.8 mL, 0.96 mmol) and chloroform(30 mL) was added to the reaction vessel,Argon gas for 25 minutes,It was then refluxed at 65 C for 12 h.After cooling to room temperature (about 25 C),The reaction product was poured into 200 mL of methanol and filtered.The obtained precipitate was sieved on a silica gel column (using 200-300 mesh silica gel,The eluent is a petroleum ether/dichloromethane in a volume ratio of 1:2 for chromatographic separation.Obtained a blue solid (147 mg, yield: 89.1%).That is, the poly-fused ring conjugated macromolecule represented by the formula (1-8-a-3).

Statistics shows that 2-(3-Oxo-2,3-dihydro-1H-inden-1-ylidene)malononitrile is playing an increasingly important role. we look forward to future research findings about 1080-74-6.

Reference:
Patent; Peking University; Zhan Xiaowei; Zhu Jingshuai; Lin Yuze; (40 pag.)CN109651393; (2019); A;,
Nitrile – Wikipedia,
Nitriles – Chemistry LibreTexts

A common heterocyclic compound, 16588-02-6, name is 2-Chloro-5-nitrobenzonitrile, molecular formula is C7H3ClN2O2, 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. 16588-02-6.

General procedure: To solution of 1.97 mmol (1.2 eq.) of phenol 2-8, 12-13 in 3 ml dry DMSO was added 79 mg(1.2 eq.) powdered NaOH. The mixture was heated at 50C for 20 min and to the formed clearsolution 0.300 g (1.64 mmol, 1.0 eq.) of 1 was added. The reaction mixture was heated at 80C for 8h. After cooling 40 ml water was added and extracted with DCM. The organic phase was washedwith aq. NaHCO3 and water, dried over Na2SO4, filtered and evaporated in vacuo. The crudeproducts 14-20, 24-25 were purified by column chromatography (50 g silica-gel). After column theformed solid products were powdered, washed with 3 ml hot hexane and dried in vacuo.

The synthetic route of 2-Chloro-5-nitrobenzonitrile has been constantly updated, and we look forward to future research findings.

Reference:
Article; Dobrikov, Georgi M.; Slavchev, Ivaylo; Nikolova, Ivanka; Stoyanova, Adelina; Nikolova, Nadya; Mukova, Lucia; Nikolova, Rosica; Shivachev, Boris; Galabov, Angel S.; Bioorganic and Medicinal Chemistry Letters; vol. 27; 19; (2017); p. 4540 – 4543;,
Nitrile – Wikipedia,
Nitriles – Chemistry LibreTexts