Month: November 2020

1953-99-7, 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.

Compound 3 was synthesized according to the reported procedure[27]. To the solution of tetrachlorophthalonitrile (1) (2 g,7.5 mmol) in anhydrous DMF (15 ml), 3-(diethylamino)phenol (2)(1.24 g, 7.5 mmol) was added. The reaction was allowed to stir for15 min, and finely powdered anhydrous Na2CO3 (1.59 g, 15 mmol)was added in portions to the reaction mixture over 1 h with efficientstirring. Then, the mixture was stirred at 30 C for 3 h. After3 h, the reaction was cooled to room temperature, poured into icecoldwater, extracted with ethyl acetate, washed with 1 M NaOHandwashed with a brine solution. The organic layerwas dried usingNa2SO4, and the solvents were evaporated to obtain the crudeproduct. The crude product was purified by column chromatographyusing hexane-ethyl acetate (90:10) as eluent. Yield (1.9 g65percent), 1H NMR (CDCl3, 300 MHz) d, 6.99 (t, J 8.4 Hz, 1H), 6.38 (dd,J 8.4 & 2.1 Hz, 1H), 6.22 (t, J 2.1 Hz, 1H), 5.68 (dd, J 7.8 & 1.5 Hz,1H), 3.26 (q, J 6.9 Hz, 4H) 1.10 (t, J 2.1 Hz, 6H) (Fig. S1), 13C NMR(CDCl3, 75 MHz) 155.9, 152.8, 148.6, 136.2, 135.3, 132.1, 129.2, 115.7,113.6, 110.8, 106.7, 99.1, 98.03, 43.4, 11.4 (Fig. S2). FT-IR (KBr pellet)(g, cm1) 2980 (AreCeH) 2920e2880 (Aliphatic-C-H), 2235 (C^N),1280 (CeOeC) (Fig. S3). LC-MS: m/z 396 [M2] (Fig. S4).

The synthetic route of 1953-99-7 has been constantly updated, and we look forward to future research findings.

Reference:
Article; Muthukumar, Palanisamy; Kim, Hak-Soo; Jeong, Jong Woo; Son, Young-A.; Journal of Molecular Structure; vol. 1119; (2016); p. 325 – 331;,
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622-75-3, A common heterocyclic compound, 622-75-3, name is 2,2′-(1,4-Phenylene)diacetonitrile, molecular formula is C10H8N2, 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.

Complex 1 was prepared by mixing of Ag(CF3SO3) (0.0308g, 0.120mmol) and p-phda (0.0099g, 0.0634mmol) in 4mL benzene or m-xylene. After stirring for 30min, the resultant solution was introduced into a 9mm diameter glass tube and layered with n-pentane (4mL) as a diffusion solvent. After standing at room temperature for one week, colorless crystals of 1 suitable for single crystal X-ray analysis were obtained. Yield: 64.42%. Anal. Calc. for C12H8Ag2F6N2O6S2 C, 21.51; N, 4.18; H, 1.21; Found: C, 21.52;N, 4.15; H, 1.19%. IR (KBr, nu/cm-1): 2920(w), 2300(w), 2250(w),1520(w), 1420(w), 1290(s), 1260(s), 1260(s), 1170(s), 1030(s), 933(m), 783(w), 629(s), 519(m).

The synthetic route of 622-75-3 has been constantly updated, and we look forward to future research findings.

Reference:
Article; Han, Jing; Yang, Jian; Yu, Zhong; Wang, Quan-jiu; Inorganica Chimica Acta; vol. 469; (2018); p. 318 – 324;,
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103146-25-4, 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. 103146-25-4, name is 4-(4-(Dimethylamino)-1-(4-fluorophenyl)-1-hydroxybutyl)-3-(hydroxymethyl)benzonitrile, This compound has unique chemical properties. The synthetic route is as follows.

Experiment 28; Experiment 11 was repeated except that the crystallization mixture did not contain toluene, a mixture of 1-propanol and dichloromethane (85:15) was used as the solvent in stead of 1-propanol in a total volume of 4.5 V, 0.5 eq of (+)-O,O’-di-p-toluoyl-(S,S)-tartaric acid was used, and the holding time before filtration was overnight.Molar yield: 37.8%, enantiomeric purity: 98.8% S.; Experiment 38; A range of experiments were conducted examining the resolution of diol with (+)-(S,S)-DTT. The general procedure is described below, and the details and results for each reaction are in table 1.Racemic diol (20 g, 58.4 mmol) was dissolved in approximately half of the solvent used for the experiment at 40 C. (+)-(S,S)-DTT.H2O (quantity specified in the table) was added as a solution in the other half of the solvent. The solution was held at 40 C. and was seeded within two minutes with crystals of (S)-diol.?(+)-(S,S)-DTT (approximately 5 mg). Crystallization typically began within 5-10 minutes after seeding. After 2 h at 40 C., the temperature of the solution was lowered to 20 C. over 2 h, and the solution was held at this temperature for a further 1 h. The product was then separated by filtration, washed with the appropriate solvent (2¡Á20 mL) and dried overnight at 60 C. under reduced pressure.

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; H. Lundbeck A/S; US2009/69582; (2009); A1;,
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626-17-5, Name is 1,3-Dicyanobenzene, 626-17-5, 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.

EXAMPLE 11; The hydrogenation was conducted in the same manner as in Example 2 except for changing the starting solution to a mixture of 1 part by weight of the starting isophthalonitrile, 8 parts by weight of liquid ammonia and 1 part by weight of m-xylene. The first hydrogenation product solution discharged from the reaction tube A was sampled just before entering into the reaction tube B and analyzed by a gas chromatography. The conversion of the starting isophthalonitrile was 95.4 mol %, the selectivity of m-xylylenediamine was 84.5 mol %, and the selectivity of 3-cyanobenzylamine was 6.20 mol %. In addition, 83.6% of the total nitrile groups in the starting isophthalonitrile were hydrogenated to aminomethyl groups in the hydrogenation step 1. The second hydrogenation product solution and unreacted hydrogen gas were discharged from the outlet of the reaction tube B. The discharged second hydrogenation product solution was sampled and analyzed by a gas chromatography. The amount of 3-cyanobenzylamine was 0.057% by weight on the basis of the weight of m-xylylenediamine. The conversion of isophthalonitrile was 99.9 mol % or more, the selectivity of m-xylylenediamine was 90.6 mol % and the selectivity of 3-cyanobenzylamine was 0.0530 mol %, each being the overall value throughout the hydrogenation step 1 and the hydrogenation step 2. After evaporating off ammonia from the second hydrogenation product solution, the crude m-xylylenediamine was distilled under reduced pressure (125 C., 6 Torr). The purified product contained 99.94% by weight of m-xylylenediamine and 580 ppm by weight of 3-cyanobenzylamine when determined by a gas chromatography.

Statistics shows that 1,3-Dicyanobenzene is playing an increasingly important role. we look forward to future research findings about 626-17-5.

Reference:
Patent; Kumano, Tatsuyuki; Shigematsu, Ryusuke; Kato, Kinji; Nakaya, Kenji; US2008/9654; (2008); A1;,
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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. 2032-34-0, name is 3,3-Diethoxypropanenitrile belongs to nitriles-buliding-blocks compound, it is a common compound, a new synthetic route is introduced below. 2032-34-0

General procedure: Add (0.5 g, 2.8 mmol) aldehyde in a stirred mixture of potassium tertiary-butoxide (0.60 g, 4.23 mmol) and 3, 3,-diethoxypropionitrile(0.63 g, 5.64 mmol) in 5 ml THF. Reflux the reaction mixture for overnight at 60 C, add 20 ml water to the solution and the mixture after cooling. It was extracted with diethyl ether. The organic phase was washed with water, sodium bicarbonate and then brine solution androtary evaporated under vacuum to get reddish oil. Then 20 ml of hydrochloric acid solution (1 M) was added and the solution was refluxedffior 1 h, neutralized and extracted with diethyl ether. The combined organic phase was washed with saturated NaOH solution. The product obtained was puriffied by using hexane/ethyl acetate system by column chromatography.3.2. Synthesis of (E)-3-(4-(diethylamino) phenyl)-2-formylacrylonitrile Red crystalline solid. Yield-68%.Melting point-96-98 C1HNMR (500 MHz, CDCl3): delta = 9.47 (s, 1 H), 7.95 (d, J=8.5 Hz,2 H), 7.65 (s, 1 H), 6.71 (d, J=8.5 Hz, 2 H), 3.49 (q, J=7.0 Hz, 4 H),1.26 (t, J=7.0 Hz, 6 H).13CNMR (126 MHz, CDCl3): delta =187.70, 157.64, 152.43, 135.04,118.91, 116.51, 111.47, 103.65, 44.97, 12.53.CHN analysis: Expected: C, 73.66; H, 7.06; N, 12.27; Results: C,73.62, H, 7.05 N, 12.29. Molecular formula: C14H16N2OFT-IR: 1668(C=O stretch), 2218 (C?N stretch), 1474(Ar-C=Cstretch), 1607(C=C stretch)Mass: Calculated 228.1263 for C14H16N2O found 229.1327 (M+1)

The synthetic route of 2032-34-0 has been constantly updated, and we look forward to future research findings.

Reference:
Article; Bhalekar, Sulochana; Avhad, Kiran; Sekar, Nagaiyan; Journal of Photochemistry and Photobiology A: Chemistry; vol. 371; (2019); p. 223 – 237;,
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194853-86-6, 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. 194853-86-6 name is 4-Fluoro-2-(trifluoromethyl)benzonitrile, 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.

Example 19; 4-(4,4-dimethyl-2,5-dioxo-3-{9-[(4,4,5,5,5-pentafluoropentylsulphanyl]nonyl}imidazolidin-1-yl)-2-(trifluoromethyl)benzonitrile19.1) 4-(4,4-dimethyl-2,5-dioxoimidazolidin-1-yl)-2-(trifluoromethyl)benzonitrileA mixture of 4-fluoro-2-(trifluoromethyl)benzonitrile (5.67 mg, 30 mmoles), 5,5-dimethyl-hydantoin (7.68 g, 60 mmoles), K2CO3 (8.28 g, 60 mmoles) in DMF (45 ml) is distributed in equal parts into three tubes to be placed in a microwave oven. Under magnetic stirring, each tube is irradiated at 140 C. for 20 minutes. The reaction masses are then combined, poured into water (200 ml) and extracted with AcOEt (2¡Á75 ml). The organic phases are combined, washed with salt water, dried over Na2SO4 and filtered. The filtrate is concentrated under reduced pressure and the residue crystallized from Et20 (25 ml). After recrystallization from EtOH (75 ml), the powder is filtered and dried under vacuum. The expected compound is obtained in the form of a white solid with a yield of 46% (4.1 g). Melting point: 212-213 C.1H NMR 400 MHz (DMSO-d6) delta: 8.80 (s, 1H, NH); 8.29 (d, 1H, Ph); 8.18 (s, 1H, Ph); 8.02 (d, 1H, Ph); 1.42 (s, 6H, 2¡ÁCH3).

At the same time, in my other blogs, there are other synthetic methods of this type of compound, 4-Fluoro-2-(trifluoromethyl)benzonitrile, and friends who are interested can also refer to it.

Reference:
Patent; Ipsen Pharma S.A.S.; US2012/83514; (2012); A1;,
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A common heterocyclic compound, 3598-14-9, name is Phenoxyacetonitrile, molecular formula is C8H7NO, 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. 3598-14-9.

To a stirring solution of the 2-[8-(benzyloxy)quinolin-7-yl]-l-phenylethanol(0.302 mmol) in phenoxyacetonitrile (9.05 mmol, 30 eq.) at -1O0C was dropwise added cone, sulfuric acid (1.51 mmol, 5.0 eq.). On completion of addition, the reaction mixture was allowed to warm to room temperature and was stirred 16h. The reaction was then diluted with ice that was allowed to melt and was then stirred 2h. The mixture was next brought to pH=7 by the addition of saturated aqueous sodium bicarbonate solution and then diluted with water (5 mL) and extracted with ethyl acetate (2 X 5 mL). The organic layers were combined, dried (MgSO4), filtered and concentrated to give sulfuric acid mono-{7-[2-(2- phenoxy-acetylamino)-2-phenyl-ethyl]-quinolin-8-yl} ester as a yellow oil that was purified by column chromatography using 20% methanol/dichloromethane. To a stirring suspension of the sulfuric acid mono-{7-[2-(2-phenoxy-acetylamino)-2-phenyl-ethyl]-quinolin-8-yl} ester (0.089 mmol, 1.0 eq.) from the initial step in methanol (9 mL) was added 3N HCl (18 mL) and the resulting suspension was heated to 550C and stirred 2h. The reaction mixture was then cooled to room temperature and organic solvents were removed by rotary evaporation resulting in a precipitate that was filtered yielding the pure product as a yellow solid (0.059 mmol, 12% for 2 steps). HRMS: calcd for C25H22N2O3 + H+, 399.17032; found (ESI-FTMS, [M+H]l+), 399.17059.

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

Reference:
Patent; WYETH; WO2008/24922; (2008); A2;,
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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. 21524-39-0, name is 2,3-Difluorobenzonitrile, This compound has unique chemical properties. The synthetic route is as follows., 21524-39-0

3-fluoro-2-(tetrahydro-2H-pyran-4-ylamino)benzonitrile To a solution of 2,3-difluorobenzonitrile (2.8 g, 19.99 mmol) in DMSO (40 mL) was added oxan-4-amine (2.0 g, 19.77 mmol) and DIEA (6.5 g, 49.91 mmol) at room temperature. The resulting solution was stirred overnight at 120 C., cooled to room temperature, and treated with water (80 mL). The resulting solution was extracted with ethyl acetate (100 mL*3). The organic phases were combined, washed with brine and dried over sodium sulfate. The solvent was removed under reduced pressure to yield 3-fluoro-2-[(oxan-4-yl)amino]benzonitrile as black solid (3.3 g, 76%). MS: m/z=221.0 [M+H]+.

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; Merck Patent GmbH; SHERER, Brian A.; KARRA, Srinivasa; XIAO, Yufang; (407 pag.)US2016/376283; (2016); A1;,
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1558-81-2, Adding some certain compound to certain chemical reactions, such as: 1558-81-2, name is Ethyl 1-Cyano-1-cyclopropanecarboxylate, 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 1558-81-2.

To a mixture of ethyl 1-cyanocyclopropanecarboxylate (35.9mmolr 5g), dimethoxyethane (10OmL) and methanol (1OmL) was added sodium borohydride (287mmol, 10.87g) slowiy and the mixture stirred at room temperature for 18 hours. The solution was diluted with saturated sodium hydrogen carbonate slowiy and then extracted with 10% methanol / dichioromethane (x3). The organic layers were combined, dried over sodium sulphate and concentrated under vacuum to give the intermediate 1-(hydroxymethyl)cyclopropanecarbonitrite (2,36g). 1H NMR (CDCI3, 400 MHz): delta 0.99 (2H, m), 1.28 (2H1 m), 2.5 (1 H, br s), 3.62 (2H, s)

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 1558-81-2.

Reference:
Patent; N.V. ORGANON; PHARMACOPEIA, LLC; COOKE, Andrew, John; BENNETT, David, Jonathan; EDWARDS, Andrew Stanley; ROUGHTON, Andrew Laird; NEAGU, Irina; CHAN, Jui-Hsiang; HO, Koc-Kan; ANSARI, Nasrin; MORRIS, Michelle Lee; RONG, Yajing; OHLMEYER, Michael; WO2010/25179; (2010); A1;,
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873-32-5, A common heterocyclic compound, 873-32-5, name is 2-Chlorobenzonitrile, molecular formula is C7H4ClN, 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.

General procedure: (0159) Pd precatalyst (0160) Base, solvent, (0161) temperature (0162) [0043] In a flask (e.g. 25 mL tube flask) equipped with a stir bar anda nitrogen pad was added an aryl halide (e.g. 1.0 mmol), an arylboronic acid (e.g. 1.1 mmol, 1.1 equiv.), octadecanol (internal standard, e.g. 0.50 mmol, 0. 50 equiv.), an organic solvent (e.g. 5 mL), water (e.g. 1 mL), and a base (e.g. 2.2 mmol, 2.20 equiv.). The mixture was purged with nitrogen (e.g. for 10 min), then a palladacycle precatalyst (e.g. 1 – 3 mol%) was added and the resulting mixture was stirred under nitrogen at the temperature indicated in the table below until the reaction was deemed complete by H NMR analysis. Aliquots (-0.05 mL) were immediately diluted with CDCb and analyzed by H NMR spectroscopy to determine the conversion and yield (yield was determined against the internal standard, (0163) octadecanol). Table 1 shows data for Suzuki couplings conducted according to the scheme above using the stated precatalysts. Entries 6, 8, and 9 are comparative. Tables 2 and 3 show data for Suzuki couplings conducted according to the scheme above using precatalyst 3.

The synthetic route of 873-32-5 has been constantly updated, and we look forward to future research findings.

Reference:
Nitrile – Wikipedia,
Nitriles – Chemistry LibreTexts