Month: March 2021

Reference of 6574-99-8, These common heterocyclic compound, 6574-99-8, name is 3,4-Dichlorobenzonitrile, 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: Hydrogen chloride gas was passed through a solution of 4-chlorobenzonitrile (9b, 25.0 g) in chloroform (350 mL) and ethanol (100 mL) at -78 C for 0.5 h. Then the solution was warmed up to room temperature, and stirred at room temperature overnight. The solution was evaporated in vacuo, and the resulting residue was dissolved with ethanol (500 mL). To the solution was added ammonium carbonate (90.0 g), and the reaction mixture was stirred at room temperature for 3 days. To the mixture was added water (300 mL), and ethanol was removed by concentration in vacuo. The resulting solid was collected by filtration, washed with water and dried in vacuo to give 12b (25.4 g, 71%) as a white solid.

Statistics shows that 3,4-Dichlorobenzonitrile is playing an increasingly important role. we look forward to future research findings about 6574-99-8.

Reference:
Article; Negoro, Kenji; Yonetoku, Yasuhiro; Misawa-Mukai, Hana; Hamaguchi, Wataru; Maruyama, Tatsuya; Yoshida, Shigeru; Takeuchi, Makoto; Ohta, Mitsuaki; Bioorganic and Medicinal Chemistry; vol. 20; 17; (2012); p. 5235 – 5246;,
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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 1835-65-0 as follows. name: 3,4,5,6-Tetrafluorophthalonitrile

With reference to Compounds 17 and 18, an exemplary synthesis and characterization of F34PcCo (hereinafter “Compound 17”) and F52Pc’Co (hereinafter “Compound 18”) is depicted. In particular, Compounds 17 and 18 are prepared similarly to Compounds 15 and 16, using sixteen (16) glass vessels, each charged with about 0.3 g (about 0.47 mmol) of Compound 14, about 0.05 g (about 0.25 mmol) of Compound 13 and about 0.045 g (about 0.18 mmol) cobalt(II) acetate tetrahydrate. Microwave heating is performed for approximately 12 min at about 185 ¡ãC. Initial purification of the brute solid by gel filtration is done with a toluene hexane approximately 1 :9 mixture (v/v). The rest of the separations are carried out as described for Compounds 1 and 16. Evaporation of the eluted fractions and drying to constant weight allows for isolation of green exemplary F52Pc’Co (Compound 18) in about 1.5percent yield (about 0.05 g), exemplary F34PcCo (Compound 17) in about 1 1 percent yield (about 0.19 g) and exemplary F]6PcCo as a side product in about 10percent yield (about 0.084 g), based on starting material Compound 13. About 4.5 g of Compound 14 are recovered following the initial separation (about 90percent of initial amount). X-ray quality single crystals for exemplary F34PcCo are obtained by slow evaporation of an acetonitrile/toluene approximately 1 :1 solution.[00106] Specifically, the exemplary properties of Compound 17, i.e., F34PcCo, are as follows: Mp > 300 ¡ãC; UV-vis (CHCI3): lmm (log e) 680 (4.52), 667 (4.50), 61 1 (4.03) nm (L moF1 cm-1); 19F NMR (282 MHz, (CD3)2CO): delta -63.58 (3F, br, GF3), -67.36 (3F, s, CF3), -68.75 to -76.79 (12F, m, CF3), -100.98 (I F, br, Ar-F), -132.36 (I F, s, CF), -137.64 (I F, d, Ar-F), -139.44 to -142.63 (5F, m, Ar-F), -155.92 to -157.62 (6F, m, Ar-F), -165.55 (I F, d, CF), -169.46 (IF, br, CF); HRMS (APCI-): calcd. for [M]~ (C41F34N8C0) 1308.9040, found 1308.9032.[00107] With reference to FIG. 17, the measured exact mass spectrum (negative ion APCI) and isotope pattern of [M]~ for F34PCC0 are depicted, indicating the calculated value for [M]~.[00108] Turning now to FIG. 18(a), the side view of the aggregation in solid state of F34PCC0 is illustrated. In particular, the toluene molecules in the crystalline lattice and the H atoms of coordinated acetonitrile have been omitted and the Z-C3F7 groups are depicted as van der Waals spheres. The interplanar stacking distance, approximately 3.25 A, illustrates the existence of pi-pi interactions. With reference to FIG. 18(b), a top view of the pi-pi stacking region of two adjacent molecules of F34PCC0 is depicted.[00109] With reference to FIG. 19, the X-ray structure of F34PcCo(CH3CN) is depicted, showing a metal-coordinated acetonitrile molecule. In particular, the thermal ellipsoids are plotted at about 40percent probability and rotational disorder of the CF3 groups of -C3F7 is present, as is shown by the dashed lines.[00110] Further, the exemplary properties of Compound 18, i.e., Fs2Pc’Co, are as follows: Mp > 300 ¡ãC; UV-vis (CHC13): max (log e) 686 (4.62), 615 (4.1 8), 334 (4.58) nm (L mol”1 cm”1); l9F NMR (282 MHz, (CD3)2CO): delta -63.62 (3F, br, C73/4, -67.01 to -76.28 (33F, m, CF3), -90.0 to -1 10.0 (2F, br, Ar-F), -137.5 to -147.5 (6F, m, Ar-F), -155.0 to – 1 59.5 (4F, br, Ar-F), -165.82 (I F, m, CF), -169.76 to -171.73 (3F, m, CF); HRMS (APC1-): calcd. for [M]~ (C5oF52NgCor 1758.8753, found 1758.8763.[00111] With reference to FIG. 20, the measured exact mass spectrum (negative ion APCI) and isotope pattern of [M]~ for F52Pc’Co are depicted, indicating the calculated value for [Mf.[00112] Turning now to FIG. 21 (a), a ball-and-stick representation ofF34PcZn(H20)*((CH3)2CO)2 is depicted showing H-bonding between the H atoms of H20 and the oxygen atoms (02) of the two acetone molecules. FIG. 21(b) is a van der Waals representation of the exemplary F3 PcZn(H20)*((CH3)2CO 2. FIG. 21(c) illustrates the side view of the aggregation in solid state of exemplary p34PcZn. The acetone molecules in the crystalline lattice and the H atoms of coordinated H2O have been omitted for clarity. The i-C3F7 groups are depicted as van der Waals spheres. The interplanar stacking distance, about3.393 A, demonstrates the existence of pi-pi interactions. Further, FIG. 21 (d) illustrates a top view of the pi-pi stacking region of two adjacent molecules of exemplary F34PCZ11. [0PsiPi3] Turning now to FIG. 22, the X-ray structure of F3 Pc2n(H20) is illustrated, showing a metal -coordinated water molecule. In particular, the acetone molecules in the crystalline lattice have been omitted. The thermal ellipsoids of FIG. 22 are plotted at about 40percent probability.

According to the analysis of related databases, 1835-65-0, the application of this compound in the production field has become more and more popular.

Reference:
Patent; NEW JERSEY INSTITUTE OF TECHNOLOGY; GORUN, Sergiu, M.; LOAS, Andrei, Ioan; GRISWOLD, Kimberly; LAPOK, Lukasz; PATEL, Hemantbhai, Hasmukhbhai; GERDES, Robert; WO2012/61344; (2012); A1;,
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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 103146-25-4 as follows. Safety of 4-(4-(Dimethylamino)-1-(4-fluorophenyl)-1-hydroxybutyl)-3-(hydroxymethyl)benzonitrile

A four-necked flask equipped with stirrer and thermometer was charged with 250.0 g of a solution of 25.0 g (0.073 mol) of [()-4- [4-DIMETHYLAMINO-L- (4′-FLUOROPHENYL)-L-] hydroxybutyl] -3-hydroxymethylbenzonitrile in toluene, and the temperature thereof was controlled so as to be [40C.] Then, 5.77 g (0.073 mol) of pyridine, 8.33 g (0.073 mol) of vinyl butyrate, 9.93 g (0.073 mol) of o-toluic acid, and 5.0 g of an immobilized enzyme (Novozym 435) was added into the above mixture. The reaction mixture was stirred at [40C] for 21 hours under a slight flow of nitrogen, and then stirring was stopped. The enzyme was filtrated from the reaction mixture with Kiriyama [FUNNEL,] and washed with 54.1 g of toluene. As a result, a toluene layer containing (S)-4- [4-dimethylamino-1- (4′-fluorophenyl)-1-hydroxybutyl]- 3-hydroxymethylbenzonitrile (9.7 g, 0. [028] mol, yield: 38.8%, optical purity: 97.8% ee), o-toluic acid salt was obtained. The combined toluene layer was washed three times with water (250 ml, 63 ml, 63 ml) at [60C,] and an aqueous layer containing [(S)-4- [4-DIMETHYLAMINO-L- (4′-] [FLUOROPHENYL)-L-HYDROXYBUTYL]-3-LIYDROXYMETHYLBENZONITRILE] (7.8 g, 0.0228 mol, extraction yield: 80%), o-toluic acid salt was obtained.

According to the analysis of related databases, 103146-25-4, the application of this compound in the production field has become more and more popular.

Reference:
Patent; H. LUNDBECK A/S; WO2004/14821; (2004); A1;,
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Related Products of 38469-83-9, 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. 38469-83-9 name is 4-Methoxy-2-nitrobenzonitrile, 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.

Intermediate 3 : 2-Iodo-4-methoxybenzonitrile; To a solution of 4-methoxy-2-nitrobenzonitrle (5.00 g, 22.46 mmol) in EtOH (93 mL) was added 5% Pd-C (0.500 g) under nitrogen atmosphere. The resulting mixture was hydrogenated at 1 atm. After stirring for 1 O h, the mixture was filtered through celite, washed with EtOAc/MeOH. The combined filtrates were concentrated in vacuo and the residue was purified by column chromatograph on SiO2 using 80 to 100 % gradient of EtOAc in hexanes to afford 4-methoxy-2-amiobenzonitrle (3.23 g, 99%). 4-Methoxy-2-aminobenzonitrle (1.0 g, 6.58 mmol) was dissolved in a mixture of H2O (7 niL), acetic acid (7 niL), and cone. HCl at rt, followed by addition of a solution Of NaNO2 (0.513 g, 7.43 mmol) in H2O (2 niL) at 0 0C for 5 min. To the above mixture KI (2.18 g, 13.2 mmol) was added and after stirring for 10 h at rt, the resulting mixture was treated with solid NaHSO3 and diluted with water. The product portion was extracted with CH2Cl2, washed with satd. NaHCO3, brine, dried (Na2SO4), filtered, and concentrated in vacuo. The residue was purified by column chromatography on SiO2 using 10 to 50% gradient of EtOAc in hexane to provide the example intermediate (1.0 g, 59%).

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

Reference:
Patent; MYRIAD GENETICS, INC.; WO2009/65035; (2009); 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. 149793-69-1, name is 3-Fluoro-5-(trifluoromethyl)benzonitrile, This compound has unique chemical properties. The synthetic route is as follows., Safety of 3-Fluoro-5-(trifluoromethyl)benzonitrile

Synthesis of Intermediate (1)Molecular Weight: 189.1 Molecu lar Weight: 247.2[00495] In a 3-neck 100 mL round-bottomed flask, to a solution of propan-2-ol (1.6 mL, 1 eq.) in DMF (25 mL, 5 V) at 0 C was added 60 % NaH in mineral oil (1.5 g, 3 eq.). The reaction mixture was stirred at 0 C for 1 h and then 3-fluoro-5-(trifluoromethyl)benzonitrile (5 g, 1.25 eq.) was added and reaction was heated to 60 C for 2 h an further stirred for 12 h at room temp. Reaction completion was monitored on TLC using ethyl acetate: hexane (2:8) as mobile phase. The reaction mixture was quenched into the ice-water slurry (250 mL) and was extracted with ethyl acetate (50 mL x 3). Organic layer was washed with brine solution (50 mL x 3). The organic layer was dried using anhydrous sodium sulfate, filtered, and concentrated under reduced pressure to provide the 5.8 g crude titled compound, yield (96 %). This crude material was directly used for next step without purification.

According to the analysis of related databases, 149793-69-1, the application of this compound in the production field has become more and more popular.

Reference:
Patent; KARYOPHARM THERAPEUTICS, INC.; SHECHTER, Sharon; KAUFFMAN, Michael; SANDANYAKA, Vincent, P.; SHACHAM, Sharon; WO2011/109799; (2011); A1;,
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Reference of 40497-11-8, 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. 40497-11-8, name is Ethyl 2,3-dicyanopropanoate belongs to nitriles-buliding-blocks compound, it is a common compound, a new synthetic route is introduced below.

Into a 500 ml three-necked glass bottle, 30.4 g (0.2 mol) of ethyl 2,3-dicyanopropionate (1E) and 300 g of water were sequentially added.The temperature of the reaction solution was lowered to 0 10 with stirring;Add 32g (0.2mol) bromine (Br2) to the reaction solution dropwise, and control the drop rate so that the solution temperature does not exceed 10 ;At the end of the dropwise addition, continue to hold at 0-10 C and stir the reaction for 4h.Then, let stand and dispense. Sampling the organic layer for gas chromatography analysis,The results showed that the content of ethyl 2-bromo-2,3-dicyanopropionate (1F), the target product of this reaction, was 91.22%, and it could be directly put into the next reaction.

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, Ethyl 2,3-dicyanopropanoate, other downstream synthetic routes, hurry up and to see.

Reference:
Patent; Jiangsu Guangyu Chemical Co., Ltd.; Shi Haibing; Song Qifa; Cai Yichao; (8 pag.)CN111004250; (2020); A;,
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Electric Literature of 3598-14-9,Some common heterocyclic compound, 3598-14-9, name is Phenoxyacetonitrile, molecular formula is C8H7NO, 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.

(4) In a 1L hydrogenation tank, 100g of phenoxyacetonitrile and 3g of Raney-Ni, 400mL of ethanol are added and H2 is continuously charged, so that the pressure of the system during the reaction is always maintained at 7MPa. After the reaction was performed at a reaction temperature of 90C for 1 hour, the temperature was lowered. After the temperature in the reactor was lowered to room temperature, the mixture was purged, and phenoxyethylamine (purity of 99% or more) was obtained by filtration and recrystallization. The yield was 93% by weight.

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

Reference:
Patent; Sinopec Corporation; Sinopec Yangzi Petrochemical Co., Ltd.; Sun Hailong; Wei Yanyu; Gao Yilong; Chen Xinhua; Miao Jun; Li Na; Kan Lin; Bai Jiye; Chen Shaohui; Yang Aiwu; Xu Yuexing; (84 pag.)CN104557610; (2018); B;,
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Electric Literature of 79463-77-7, 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. 79463-77-7, name is Diphenyl N-cyanocarbonimidate belongs to nitriles-buliding-blocks compound, it is a common compound, a new synthetic route is introduced below.

Alternatively, a mixture of 2n (4.46 g, 21.3 mmol) and diphenylcyanocarbimidate (5.07 g, 21.3 mmol) in 2-PrOH (100 mL) was stirred at ambient temperature under N2 for 20 h. The solids that formed were collected by filtration and washed with 2-PrOH to afford 3k (5.90 g, 78%) as an off-white solid: 1H NMR (300 MHz, DMSO-d6) delta 10.82 (s, 1 H), 7.50-7.37 (m, 2H), 7.32-7.26 (m, 4H), 7.08-7.03 (m, 2H), 6.82 (dd, J = 7.9, 1.9 Hz, 1H), 4.98 (t, J = 4.9 Hz, 1 H), 4.07 (t, J = 6.5 Hz, 2H), 3.93-3.76 (m, 4H), 2.06-2.00 (m, 2H).

The synthetic route of Diphenyl N-cyanocarbonimidate has been constantly updated, and we look forward to future research findings.

Reference:
Patent; RIGEL PHARMACEUTICALS, INC.; WO2007/30680; (2007); 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. 89001-53-6, name is 2-Methyl-4-nitrobenzonitrile, This compound has unique chemical properties. The synthetic route is as follows., Recommanded Product: 2-Methyl-4-nitrobenzonitrile

Intermediate IA: (?)-2-(2-(Dimethylammo)vinyl)-4-nitrobenzonitrile; [00186] A mixture of 2-methyl-4-nitrobenzonitrile (5.0 g, 31 mmol) and tert- butoxybis(dimethylamino)methane (12.2 mL, 59 mmol) in dry DMF (8 mL) was stirred at 70 C for 2 h under N2. After cooling to it, DMF was removed in vacuo and the crude product was triturated with hexanes/EtOAc (5:1). The solid was collected by filtration and washed with hexane to give Intermediate IA (6.5 g, 97%) as black solid. 1HNMR (400 MHz, CDCl3) delta 2.97 (s, 6H), 5.36 (d, J = 13.2 Hz, IH), 7.16 (d, J= 13.6 Hz, IH), 7.52 (d, J= 8.8 Hz, IH), 7.60 (m, IH), 8.11 (d, J= 1.8 Hz, IH).

According to the analysis of related databases, 89001-53-6, the application of this compound in the production field has become more and more popular.

Reference:
Patent; BRISTOL-MYERS SQUIBB COMPANY; WO2007/76431; (2007); A1;,
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Application of 51762-67-5, A common heterocyclic compound, 51762-67-5, name is 3-Nitrophthalonitrile, molecular formula is C8H3N3O2, 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.

The synthetic procedure was adopted from Mayukh etal. with some modifications [37]. A mixture of 4-mercaptophenol (1.26g, 0.01mol) and K2CO3 (4.15g, 0.03mol) in dry dimethylformamide (DMF) (25mL) was stirred vigorously in nitrogen atmosphere for 30min and then 3-nitrophthalonitrile (1.75g, 0.01mol) was added into the reaction mixture followed by a stirring for 16h at 90C. The reaction mixture was allowed to cool room temperature and poured into 1M HCl and the precipitate formed was filtered off and washed with water until the filtrate was neutral and dried in vacuum. The precipitate was extracted with ethyl acetate. The combined organic phases were treated with distilled water, dried with anhydrous sodium sulfate and solvent removed under reduced pressure to obtain solid orange colored powder. The product was further purified by chromatography over a silica gel column using Ethyl acetate and hexane (3:1) mixture as eluent. Yield: 1.73g, (68%); m.p. 162-164C. FT-IR numax/cm-1; 3403 (Ar-OH), 3077-2923 (Ar-H), 2241 (C?N). 1H NMR (DMSO-d6) delta/ppm: 10.18 (s, 1H, Ar-OH), 7.84 (d, 1H, Ar-H), 7.68 (t, 1H Ar-H), 7.42 (d, 2H, Ar-H), 7.09 (d, 1H, Ar-H), 6.91ppm (d, 2H, Ar-H); 13C NMR (DMSO-d6) delta/ppm: 160.21 (aromatic C-O), 147.51, 137.76, 134.51, 130.96, 117.97, 116.40 (C?N), 114.57, 110.27. Anal. Calcd. for C14H8N2OS (252.291g/mol); C 66.65, H 3.20, N 11.10; Found: C 66.56, H 3.09, N 11.08. MS (GC/MS): m/z: 252 [M]+.

The synthetic route of 51762-67-5 has been constantly updated, and we look forward to future research findings.

Reference:
Article; Suerguen, Serdar; Arslano?lu, Yasin; Hamuryudan, Esin; Dyes and Pigments; vol. 100; 1; (2014); p. 32 – 40;,
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