Month: May 2021

Electric Literature of 121588-79-2, A common heterocyclic compound, 121588-79-2, name is trans-4-Methoxycyclohexanamine, molecular formula is C7H15NO, 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 mixture of 5-chloro-6-ethyl-3-{3-methoxy-4-[4-(4-methylpiperazin-1-yl)piperidin-1-yl]anilino}pyrazine-2-carboxamide (11,100 mg, 0.205 mmol) and NMP (1.5 mL) was added (1r,4r)-4-methoxycyclohexan-1-amine (106 mg, 0.820 mmol), and the mixture was irradiated with microwaves at 200 C for 30 min. After the mixture was cooled, saturated aqueous NaHCO3 solution was added, and the resulting slurry was extracted with EtOAc. The organic layer was washed with brine, dried over anhydrous MgSO4, and concentrated in vacuo.The residue was purified by silica gel column chromatography (CHCl3/MeOH/28% aqueous NH3=100:0:0 to 200:10:1). The resulting product was solidified from EtOAc, filtered and dried to give 12c (62 mg,52%) as a yellow solid. 1H NMR (DMSO-d6): delta 1.10-1.28 (2H, m), 1.18(3H, t, J=7.4 Hz), 1.33-1.63 (4H, m), 1.73-1.86 (2H, m), 1.89-2.00(2H, m), 2.00-2.11 (2H, m), 2.14 (3H, s), 2.18-2.64 (11H, m), 2.56(2H, q, J=7.3 Hz), 3.05-3.19 (1H, m), 3.22-3.39 (2H, m), 3.26 (3H, s),3.75-3.95 (1H, m), 3.80 (3H, s), 6.66 (1H, d, J=7.6 Hz), 6.78 (1H, d,J=8.4 Hz), 7.05 (1H, d, J=2.4 Hz), 7.18 (1H, d, J=2.8 Hz), 7.24(1H, dd, J=2.4, 8.8 Hz), 7.50 (1H, d, J=2.8 Hz), 11.01 (1H, s); MS(ESI) m/z [M+H]+ 581; HRMS (ESI) m/z Calcd for C31H49N8O3[M+H]+: 581.3922, Found: 581.3924.

The synthetic route of 121588-79-2 has been constantly updated, and we look forward to future research findings.

Reference:
Article; Iikubo, Kazuhiko; Kurosawa, Kazuo; Matsuya, Takahiro; Kondoh, Yutaka; Kamikawa, Akio; Moritomo, Ayako; Iwai, Yoshinori; Tomiyama, Hiroshi; Shimada, Itsuro; Bioorganic and Medicinal Chemistry; vol. 27; 8; (2019); p. 1683 – 1692;,
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Adding a certain compound to certain chemical reactions, such as: 57602-02-5, name is 1,14-Dibromo-3,6,9,12-tetraoxatetradecane, belongs to ethers-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 57602-02-5, category: ethers-buliding-blocks

1,14-dibramo-3,6,9,12-tetraoxatetradecane (3.35 g, 9.2 mmol) and sodium methanethiosulfonate (2.48 g, 18.5 mmol) were dissolved in dry DMF (40 mL) and stirred at room temperature for 3 days. The solvent was evaporated. The residue was purified by column chromatography on SiO2. Elution with ethyl acetate/hexane (9:1) afforded, after evaporation, 1-(14-bromo-3,6,9,12-tetraoxatetradecyl) methanethiosulfonate (0.85 g) as a pale yellow oil and tetraoxatetradecane-1,14-diyl-bis-methanethiosulfonate (useful as a cross linker) as a slightly yellow colored oil (1.64 g).

At the same time, in my other blogs, there are other synthetic methods of this type of compound, 1,14-Dibromo-3,6,9,12-tetraoxatetradecane, and friends who are interested can also refer to it.

Reference:
Patent; Dime, David S.; Backx, Peter; Kimmeldirk, Klaus; EP966304; (2005); B1;,
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Application of 10578-75-3,Some common heterocyclic compound, 10578-75-3, name is 2-(Benzyloxy)ethanamine hydrochloride, molecular formula is C9H14ClNO, 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.

2,4-Dichloro-6,7-dimethyl-3-nitropyridine (26.89 g, 121.7 mmol), anhydrous N,N-dimethylformamide (400 mL), anhydrous triethylamine (48.84 mL), and the benzyloxyethylamine hydrochloride salt (27.4 g, 146.0 mmol) from Part B were combined under nitrogen and heated to 90 C. for 20 minutes, 60 C for 1 hour, and then 90 C. for 1 hour. The reaction was complete as determined by TLC analysis using 8/2 hexane/ethyl acetate. The reaction mixture was concentrated under reduced pressure, and the resulting orange solids were triturated with water. The resulting solids were filtered off and recrystallized from ethyl acetate. Recrystallized solids were rinsed with hexane and dried under vacuum at 50 C. for 30 minutes to provide 21.8 g of yellow fluffy solid for use in the next step. NMR analysis confirmed the N-[2-(benzyloxy)ethyl]-2-chloro-5,6-dimethyl-3-nitropyridin-4-amine and a minor amount of residual salts.; Under a nitrogen atmosphere, triethylamine (40.4 mL, 290 mmol) was added to a solution of 2,4-dichloro-6-methyl-3-nitropyridine (12.0 g, 58.0 mmol), prepared according to the general method of Part A of Example 1 using 2,4-dihydroxy-6-methyl-3-nitropyridine in lieu of 2,4-dihydroxy-5,6-dimethyl-3-nitropyridine, in anhydrous N,N-dimethylformamide (DMF) (200 mL). To the resulting dark brown solution was added 2-(benzyloxy)ethylamine hydrochloride (11.97 g, 63.76 mmol), and the mixture was stirred at room temperature for 23 hours. The volatiles were then removed under reduced pressure, and the residue was mixed with water and ethyl acetate. The organic layer was washed with water (3×200 mL), aqueous sodium bicarbonate (2×200 mL), and brine (3×250 mL), dried over magnesium sulfate, filtered, and concentrated under reduced pressure to provide a brown oil. The crude product (18.1 g) was purified by column chromatography on silica gel (700 g, eluting with 80:20 hexane:ethyl acetate) to provide an oil which was triturated with 80:20 hexane:ethyl acetate. The resulting crystals were isolated by filtration and dried to provide 4.7 g of [2-(benzyloxy)ethyl]-(2-chloro-6-methyl-3-nitropyridin-4-yl)amine as a yellow solid.

The synthetic route of 10578-75-3 has been constantly updated, and we look forward to future research findings.

Reference:
Patent; Dellaria, Joseph F.; Lindstrom, Kyle J.; Dressel, Luke T.; Duffy, Daniel E.; Heppner, Philip D.; Jacobsen, John R.; Moseman, Joan T.; Moser, William H.; Radmer, Matthew R.; Stoermer, Doris; Zimmermann, Bernhard M.; US2004/10007; (2004); A1;,
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Reference of 104750-60-9, 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. 104750-60-9, name is 2-Bromo-1-(methoxymethoxy)-4-methylbenzene belongs to ethers-buliding-blocks compound, it is a common compound, a new synthetic route is introduced below.

General procedure: 4-(2-hydroxy-5-methylphenoxy)-3-methoxybenzoic acid (18o). The bromination of p-cresol, carried out via the method of Narender, et al.,3 was followed by MOM protection4 (96% yield over two steps). A solution of bis(pinacolato)diborane (2.5 g), dioxane (40 mL), KOAc (2.5 g) and the aryl bromide (6.5 mmol) was purged with nitrogen before Pd(dppf)Cl2 (0.47 g) was added. The mixture was refluxed overnight. Silica chromatography (gradient to 20% EtOAc/hexanes) gave the boronate ester (1.93 g), which was dissolved in acetone (20 mL) and treated with a solution of Oxone (4 g) in H2O (20 mL). After 10 min, NaHSO3 was added and the resulting solution was extracted with EtOAc. Silica chromatography (gradient up to 15% EtOAc/hexanes) gave 2-(methoxymethoxy)-5-methylphenol (0.578 g, 53% over two steps). The diaryl ether was prepared from the phenol and appropriate 4-fluorobenzalde using General Procedure D. Silica chromatography (gradient up to 40% EtOAc/hexanes) gave the intermediate aldehyde (481 mg, 47%). The oxidation was followed by MOM cleavage with conc. HCl (0.25 mL) in 50% THF/iPrOH (10 mL) to yield 18o (391 mg, 89% over two steps). 1H NMR (CDCl3) delta 7.73-7.66 (m, 2H), 6.99-6.85 (m, 3H), 6.76 (s, 1H), 3.97 (s, 3H), 2.24 (s, 3H).

The synthetic route of 2-Bromo-1-(methoxymethoxy)-4-methylbenzene has been constantly updated, and we look forward to future research findings.

Reference:
Patent; RESEARCH TRIANGLE INSTITUTE; Carroll, Frank I.; Thomas, James B.; Navarro, Hernan A.; Mascarella, S. Wayne; Runyon, Scott P.; Jin, Chunyang; Kormos, Chad M.; (20 pag.)US9512105; (2016); B2;,
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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. 17600-72-5, name is 1-Ethoxy-2-methoxybenzene, A new synthetic method of this compound is introduced below., Recommanded Product: 17600-72-5

10 g of the compound obtained in the preceding stage are cooled to -10 C., 21.84 ml of chlorosulfonic acid and then 13.68 g of phosphorus pentachloride are added dropwise and the mixture is left stirring at -5 C. for 1 hour. The reaction mixture is run onto 250 ml of ice and water and extracted with DCM, the organic phase is dried over Na2SO4 and the solvent is evaporated under vacuum. The residue is chromatographed on silica gel, elution being carried out with the gradient of the cyclohexane/AcOEt mixture from 95/5 (v/v) to 85/15 (v/v). The expected compound is obtained, M.p.=93 C. 1H NMR: CDCl3 (250 MHz): delta (ppm): 1.55, t, 3H, 3.99, s, 3H, 4.23, q, 2H, 6.97-7.02, mt, 1H, 7.46-7.48, mt, 1H, 7.66-7.71, mt, 1H.

The synthetic route of 17600-72-5 has been constantly updated, and we look forward to future research findings.

Reference:
Patent; SANOFI-AVENTIS; US2011/59955; (2011); A1;,
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Application of 172282-50-7,Some common heterocyclic compound, 172282-50-7, name is 4-(Difluoromethoxy)benzene-1,2-diamine, molecular formula is C7H8F2N2O, 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.

In a mechanical stirrer, Reflux condenser, the thermometer of the four-mouth flask, with lye:Sodium carbonate 6. 6 grams + 20 grams of tap water,Stirring to dissolve, slightly cooling, adding4-difluoromethoxy-o-phenylenediamine 34. 8 g,Stir for 20 min. Heated to 30 C,25-35 C20 g of carbon disulfide was added dropwise,Drop finished 30-40 C insulation condensation 6h,Continue to heat up to 60-70 C insulation 6h, cyclization is complete, add activated carbon decolorization,The filtrate was adjusted to pH 5-6 with sulfuric acid, filtered, washed, dried,5-difluoromethoxy-2-mercapto-1H-benzimidazole was obtained in an amount of 33.2 g,The yield was 95.4% based on 4-difluoromethoxy-o-phenylenediamine.

These compound has a wide range of applications. It is believed that with the continuous development of the source of the synthetic route 4-(Difluoromethoxy)benzene-1,2-diamine, its application will become more common.

Reference:
Patent; ZHEJIANG UNIVERSITY OF SCIENCE AND TECHNOLOGY; JIANGSU YUXIANG CHEMICAL CO., LTD; ZHANG, ZHIGUO; CHENG, YUNTAO; ZHONG, XUHUI; LI, QINGLONG; CHENG, HONGWEI; (6 pag.)CN103539746; (2016); B;,
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Synthetic Route of 14093-86-8, The chemical industry reduces the impact on the environment during synthesis 14093-86-8, name is 1-Methoxy-2-methylnaphthalene, I believe this compound will play a more active role in future production and life.

Example 1 In a four-necked, round-bottomed flask fitted with a stirrer, a thermometer, a cooler and a dropping funnel, were placed 0.5 g of potassium ferricyanide, 17.2 g of 1-methoxy-2-methylnaphthalene (90% content), 10 ml of water and 100 ml of glacial acetic acid. The mixture was heated with stirring, and dropping of 35% hydrogen peroxide was started when the internal temperature reached 55C, with the total amount (33 g) being added over a period of one hour. Stirring was further continued for four hours while maintaining the internal temperature within the range of 50 to 60C. High-performance liquid chromatography (HPLC) was used to confirm the consumption of 1-methoxy-2-methylnaphthalene. At the end of reaction, 200 ml of hot water (about 50C) was added and the resulting mixture was extracted twice with 200 ml each of isopropylether. To the combined extracts were added 200 ml of n-hexane and 5 g of activated charcoal, the mixture was stirred at 50C for 30 minutes, and the insoluble matters and activated charcoal were filtered off. The filtrate was dried over anhydrous magnesium sulfate and concentrated, giving 9.5 g (61.0%) of 2-methyl-1,4-naphthoquinone as yellow crystals. The purity was 98.8% when measured by HPLC (relative peak-area method; UV detection at 254 nm).

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, 1-Methoxy-2-methylnaphthalene, other downstream synthetic routes, hurry up and to see.

Reference:
Patent; Eisai Chemical Co., Ltd.; EP247513; (1991); B1;,
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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. 706-27-4, name is 4-(Trifluoromethoxy)toluene belongs to ethers-buliding-blocks compound, it is a common compound, a new synthetic route is introduced below. Formula: C8H7F3O

Example 38 6-Trifluoromethoxy-1H-indole Combine 1-methyl-4-trifluoromethoxybenzene (5.44 g, 30.87 mmol) and H2SO4 (96%, 30.9 ml). Cool to about 0C. Add dropwise fuming HNO3 (2.06 g, 32.72 mmol) while maintaining the temperature below 10C. When the addition is complete, warm to ambient temperature. After 2.5 hours, pour the mixture onto ice/water, extract with dichloromethane. Combine the organic extracts, wash with brine, dry (Na2SO4), then concentrate to residue. Chromatograph the residue on silica gel eluting with hexanes/ethyl acetate (75/25) to give, after evaporation, 1-methyl-2-nitro-4-trifluoromethoxybenzene: MS (ACPI): m/e 220.1 (M-1).

The synthetic route of 706-27-4 has been constantly updated, and we look forward to future research findings.

Reference:
Patent; ELI LILLY AND COMPANY; Chen, Zhaogen; Cohen, Michael Philip; Fisher, Matthew Joseph; Gillig, James Ronald; McCowan, Jefferson Ray; Miller, Shawn Christopher; Schaus, John Mehnert; Giethlen, Bruno; (141 pag.)EP1859798; (2015); B1;,
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Application of 10075-63-5,Some common heterocyclic compound, 10075-63-5, name is 1,5-Dimethoxynaphthalene, molecular formula is C12H12O2, 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.

1Og (0.05mol) of the 1,5-dimethoxynaphthalene, synthesized in PreparationExample 1-1, was dissolved in 160 ml of acetonitrile in a 1,000 ml round-bottom flask. A solution of 21g (0.12mol) of N-bromosuccinimide (NBS) in 180ml of acetonitrile was droplet added to the flask with stirring. After stirring at room temperature for 3 hours, the vacuum filtration of the reaction mixture formed precipitates which were washed with acetonitrile and then twice with hexane and dried to give 12.7 g of the title compound as white power. The properties of the product are as described below.[112][113] Yield: 69.02%, m.p.: 187-188 0C[114] Rf: 0.20 [hexane:ethylacetate(50: 1)][115] IH-NMR (CDCl , 400MHz): delta 7.68(d, J=8.4Hz, 2H), 6.72(d, J=8.4Hz, 2H), 3.91(s,6H)

These compound has a wide range of applications. It is believed that with the continuous development of the source of the synthetic route 1,5-Dimethoxynaphthalene, its application will become more common.

Reference:
Patent; KOREA RESEARCH INSTITUTE OF BIOSCIENCE AND BIOTECHNOLOGY; WO2008/18645; (2008); A1;,
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Electric Literature of 13353-03-2,Some common heterocyclic compound, 13353-03-2, name is 2,4,6,8-Tetraoxanonane, molecular formula is C5H12O4, 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 250ml four-necked flask was added under mechanical stirring phenol (phenol and paraformaldehyde dimethyl ether molar ratio of 15:1), phosphoric acid (the molar ratio of phosphoric acid to paraformaldehyde dimethyl ether is 6.4: 1) and water (molar ratio of water and paraformaldehyde dimethyl etherRatio of 14: 1), the water bath was slowly heated to 80 C, and then 5 g of paraformaldehyde dimethyl ether was slowly added dropwise during the controlTemperature between 75 -85 C . Bi completed, maintaining the temperature at 80 C to continue the reaction 4h. Complete the reaction of raw materials, natural cooling to 45 C ,The reaction solution was poured into a separatory funnel, standing stratification, the lower phosphoric acid aqueous solution recovery applied. After the upper organic phase is neutralized by alkali,Concentrated under reduced pressure, the application of excess phenol recovery. The concentrate was diluted with ethyl acetate and washed successively with saturated aqueous ammonium chloride solutionWashed with water, dried over anhydrous sodium sulfate, suction filtered, the filtrate was concentrated to dry twice to obtain the crude product. Crude by high pressure liquid chromatographyMeasured, bisphenol F yield, selectivity and product distribution in Table 2.

These compound has a wide range of applications. It is believed that with the continuous development of the source of the synthetic route 2,4,6,8-Tetraoxanonane, its application will become more common.

Reference:
Patent; Yancheng Tonghai Biological Technology Co., Ltd.; Wang Hui; Shen Jianyi; Zhao Yupei; Zhu Jian; Wang Yang; (10 pag.)CN105152866; (2017); B;,
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