Month: February 2021

Application of 17100-65-1,Some common heterocyclic compound, 17100-65-1, name is Methyl 2-bromo-4-methoxybenzoate, molecular formula is C9H9BrO3, 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.

(0580) Methyl 2-bromo-4-methoxybenzoate (20 g, 0.082 mol) was dissolved in N,N-dimethylformamide (100 mL), and cuprous cyanide (10.95 g, 0.123 mol) was added. (0581) The reaction was carried out at 150 C. for 4 h. The mixture was cooled, and was poured into saturated ammonium chloride aqueous solution. The mixture was extracted with ethyl acetate (150 mL¡Á3). The organic phases were combined, dried with anhydrous sodium sulfate, filtrated, and concentrated. The crude product was purified by silica gel column chromatography (petroleum ether:ethyl acetate=5:1) to get the title compound (9.8 g, yield: 62%).

The synthetic route of 17100-65-1 has been constantly updated, and we look forward to future research findings.

Reference:
Patent; Xuanzhu Pharma Co., Ltd.; WU, Frank; (117 pag.)US2017/112833; (2017); A1;,
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Synthetic Route of 15963-40-3,Some common heterocyclic compound, 15963-40-3, name is Methyl 3-methylenecyclobutanecarboxylate, molecular formula is C7H10O2, 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 solution of methyl 3-methylenecyclobutanecarboxylate (5.3 g, 42.4 mmol, 1.0 eq) in THF (30 mL) was added BH3 (12.6 mL, 12.6 mmol, 0.3 eq, 1 M) dropwise at 0 C. Then the reaction mixture was warmed to ft and stirred for 4 h. MeOH (15 mL) was added and the mixture was stirred for 30 mm at 0 C. NaOH (4.2 mL, 3M) and H202 (1.4 g, 42.4 mmol, 1.0 eq) wereadded and stirred at 0 C for 1 h. The mixture was quenched with water (30 mL) and extracted with Et20 (60 mL X 2). The combined organic phases were dried over Na2SO4 After filtration and concentration, 3.3 g of methyl 3-(hydroxymethyl)cyclobutanecarboxylate as yellow oil was obtained. Y: 54%. ESI-MS (M+H): 145.0. ?H NMR (400 MHz, CD3OD) (5: 3.69 (s, 1.3H), 3.67 (s, 1.7H), 3.59 (s, 0.4H), 3.58 (s, 0.5H), 3.50 (s, 0.4H), 3.48 (s, 0.5H), 3.12-3.03 (m, 1H), 2.48-2.38 (m, 1H), 2.35-2.22 (m, 2H), 2.08-1.94 (m, 2H).

The synthetic route of 15963-40-3 has been constantly updated, and we look forward to future research findings.

Reference:
Patent; BIOGEN MA INC.; CHAN, Timothy; GUCKIAN, Kevin; JENKINS, Tracy; THOMAS, Jermaine; VESSELS, Jeffery; KUMARAVEL, Gnanasambandam; MEISSNER, Robert; LYSSIKATOS, Joseph, P.; LUCAS, Brian; LEAF, Irina; DUFFIELD, Jeremy; GENUNG, Nathan; (113 pag.)WO2017/127430; (2017); A1;,
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Synthetic Route of 7270-63-5, 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. 7270-63-5 name is 5-Diazo-2,2-dimethyl-1,3-dioxane-4,6-dione, 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.

General procedure: 1- (3,4,5-trimethoxyphenyl) hexan-1-one (3aa) (53.3 mg, 0.2 mmol, 100 mol%),[IrCp * Cl 2] 2 (3.2 mg, 0.004 mmol, 2 mol%) or[RhCp * Cl 2] 2 (2.5 mg, 0.004 mmol, 2 mol%),AgNTf2 (6.2 mg, 0.016 mmol, 8 mol%),AgOAc (2.6 mg, 0.016 mmol, 8 mol%) andIn an oven-dried sealed tube filled with 5-diazo-2,2-dimethyl-1,3-dioxane-4,6-dione (4a) (40.8 mg, 0.24 mmol, 120 mol%), EtOH (18.4 mg, 0.4 mmol, 200 mol%) and DCE (1 mL) were added in air at room temperature.The reaction mixture was stirred at 60 C for 20 h. The reaction mixture was cooled to rt, diluted with EtOAc (3 mL) and concentrated in vacuo. The residue was purified by flash column chromatography (n-hexane / EtOAc = 12: 1) to give 5aa (50.2 mg, 71%) as a yellow solid.

At the same time, in my other blogs, there are other synthetic methods of this type of compound, 5-Diazo-2,2-dimethyl-1,3-dioxane-4,6-dione, and friends who are interested can also refer to it.

Reference:
Patent; SUNGKYUNKWAN University Research & Business Foundation; Kim In-su; Kim Hyeong-sik; (40 pag.)KR2019/87836; (2019); A;,
Ester – Wikipedia,
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Reference of 42122-75-8, These common heterocyclic compound, 42122-75-8, name is Methyl 5-amino-2-chlorobenzoate, 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: To a solution 15 (490 mg, 1.0 eq, 0.92 mmol) in CH2Cl2 (50 mL) was added HATU (525 mg, 1.5 eq, 1.38 mmol), 4-methylmorpholine (0.30 mL, 3.0 eq, 2.8 mmol) and methyl 3-aminobenzoate hydrochloride (208 mg, 1.2 eq, 1.1 mmol). The reaction mixture was stirred at room temperature overnight. After the solvent was concentrated in vacuo, the residue was purified by chromatography (petroleum ether/acetone = 3/1) to afford compound 16 as white solid (360 mg, 59%).

Statistics shows that Methyl 5-amino-2-chlorobenzoate is playing an increasingly important role. we look forward to future research findings about 42122-75-8.

Reference:
Article; Chen, Yue-Ting; Tang, Chun-Lan; Ma, Wei-Ping; Gao, Li-Xin; Wei, Yi; Zhang, Wei; Li, Jing-Ya; Li, Jia; Nan, Fa-Jun; European Journal of Medicinal Chemistry; vol. 69; (2013); p. 399 – 412;,
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Synthetic Route of 2178-24-7,Some common heterocyclic compound, 2178-24-7, name is Ethyl (2-bromophenyl)acetate, molecular formula is C10H11BrO2, 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 1(4′-Methylbiphenyl-2-yl)acetic acid a) Ethyl (4′-methylbiphenyl-2-yl)acetateTo a mixture composed of 243.1 mg (1 mmol) of ethyl 2-(2-bromophenyl)- acetate, 3.7 ml of toluene, 57.8 mg (0.05 mmol) of tetrakis(triphenylphosphine)- palladium and 127.2 mg (1.2 mmol) of anhydrous sodium carbonate are added EPO 169.9 mg (1.25 mmol) of 4-methy.phenylboronic acid, followed by addition of 2.21 ml (0.055 mmol) of methanol. The reaction medium is heated at 85C for 16 hours with stirring. After cooling, 10 ml of water and 8 ml of ethyl acetate are added with stirring, and the mixture is then filtered through a fluted filter paper. The organic phase is recovered and the aqueous phase is extracted again with ethyl acetate.The combined organic phases are washed with water (2 x 10 ml), dried over Na2SO4 and then concentrated to give 310 mg of oil, which is purified by flash chromatography on a column of silica, in a dichloromethane/heptane mixture (1 :1). 201 mg of a colourless oil are obtained.Yield: 79%NMR (CDCI3): 1.2 (t, J=7.2 Hz, 3H); 2.5 (s, 3H); 3.7 (m, 2H), 4.1 (q, J=7.2 Hz, 2H); 7.3 (m, 8H).

These compound has a wide range of applications. It is believed that with the continuous development of the source of the synthetic route Ethyl (2-bromophenyl)acetate, its application will become more common.

Reference:
Patent; MERCK PATENT GMBH; WO2006/58592; (2006); A1;,
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Ester – an overview | ScienceDirect Topics

Reference of 23877-12-5,Some common heterocyclic compound, 23877-12-5, name is tert-Butyl 2-bromo-2-methylpropanoate, molecular formula is C8H15BrO2, 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.

Scheme 1. A solution of ethyl-(6-triisopropylsilanylsulfanyl-1, 2,3, 4- tetrahydro-naphthalen-2-yl)-carbamic acid 4-trifluoromethoxy-phenyl ester (260.0 mg; 0.46 MMOL) and tert-butyl 11-BROMOISOBUTYL RATE (130 uL, 0.69 MMOL) in anhydrous THF (2 mL) was cooled to 0 C, a 1.0 M solution of TBAF (690 uL, 0.69 MMOL) was added, then the reaction was warmed to RT, stirred for 1 h, and then diluted with water, extracted with Et20 (3 times). The combined organic extracts were dried over NA2SO4, and the solvent removed under reduced pressure. The crude residue was purified by flash chromatography eluting with Hexane-EtOAc (7: 1) to provide 229.2 mg (90%) of 2- {6- [ETHYL- (4-TRIFLUOROMETHOXY- PHENOXYCARBONYL)-AMINO]-5, 6,7, 8-TETRAHYDRONAPHTHALEN-2-YLSULFANYL}-2-METHYL- propionic acid tert-butyl ester as a light-color oil. 1H NMR (300 MHz, CDCI3) : S 6.95-7. 28 (m, 7 H), 4.34 (m, 1H), 3.41 (m, 2H), 2.96 (m, 2H), 2.91 (m, 2H), 3.41 (m, 2H), 2.06 (m, 2H), 1.44 (s, 6H), 1.42 (s, 9H), 1.28 (m, 3H) LC/MS: C28H34F3NO5SNA : m/z 576 (M+NA)

The synthetic route of 23877-12-5 has been constantly updated, and we look forward to future research findings.

Reference:
Patent; JANSSEN PHARMACEUTICA, N.V.; WO2004/37779; (2004); A1;; ; Patent; JANSSEN PHARMACEUTICA, N.V.; Demarest, Keith, T.; WO2004/37778; (2004); A1;,
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Synthetic Route of 3618-04-0, These common heterocyclic compound, 3618-04-0, name is trans-Ethyl 4-hydroxycyclohexanecarboxylate, 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.

Step 2 Ethyl 4-oxocyclohexanecarboxylate (33.0) STR44 To a 3-L 3-neck flask equipped with a mechanical stirrer, a thermometer, and an addition funnel were added 50 g (292 mmol) of the compound of Formula 32.0 from Step 1, 33 mL (584 mmol) of acetic acid and 145 mL of commercial bleach (5.25percent NaOCl). To the cooled reaction mixture, at 5¡ã C., was added dropwise 479 mL of more bleach. The reaction was allowed to warm to room temperature for 1 hour and then was extracted with 3*400 mL ethyl acetate. The combined extract was washed with water, dried over MgSO4, and concentrated to give 49 g of crude 33.0 as an oil which was used without purification. The spectrum data are identical to that of literature (see Sanchez, I. H.; Ortega, A.; Garcia, G.; Larraza, M. I.; Flores, H. J. Synthetic comm. 1985, 15, 141).

The synthetic route of 3618-04-0 has been constantly updated, and we look forward to future research findings.

Reference:
Patent; Schering Corporation; US5648484; (1997); A;,
Ester – Wikipedia,
Ester – an overview | ScienceDirect Topics

Related Products of 15568-85-1, 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 15568-85-1 as follows.

General procedure: 5-(Methoxymethylene)-2,2-dimethyl-1,3-dioxane-4,6-dione (0.5 g, 2.9 mmol) was added to a stirred solution of the 5-aminopyrazole 6 (2.9 mmol) in MeCN (10 mL). After stirring for 1 h, the solvent was removed in vacuo to complete the precipitation of the product.

According to the analysis of related databases, 15568-85-1, the application of this compound in the production field has become more and more popular.

Reference:
Article; Mackay, Martha; Nortcliffe, Andrew; McNab, Hamish; Hulme, Alison N.; Synthesis; vol. 47; 2; (2015); p. 242 – 248;,
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Reference of 6065-82-3, 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. 6065-82-3 name is Ethyl diethoxyacetate, 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.

TMSOTf (0.33 mL, 1.85 mmol) was added to a suspended solution of 25 (209.0 mg, 0.443 mmol) and ethyl diethoxyacetate (83.0 mL, 0.46 mmol) in dichloroethane (15 mL), and the reaction mixture was heated at 120 C for 13 h. The reaction mixture was diluted with saturated NaHCO3 (200 mL) and extracted with chloroform (3¡Á200 mL). The combined extracts were washed with brine (200 mL), dried, and concentrated in vacuo to give a residue (246 mg). Chromatography of this residue on a silica gel (120 g) column with dichloromethane-methanol (50/1) gave 26 (190.0 mg, 77.1%) as a pale yellow amorphous powder, the recrystallization of which from ethyl acetate-ether afforded 26 as colorless prisms, mp 253-254 C. IR (KBr) 3399, 2940, 1732, 1639, 1460, 1422, 1350, 1281, 1192, 1117, 1067 cm-1; 1H NMR (CDCl3, 500 MHz) delta 1.28 (3H, t, J=7.0 Hz, OCH2CH3), 2.06 (3H, s, 12-CH3), 2.11 (3H, s, 3-CH3), 2.30 (1H, dd, J=16.8, 10.4 Hz, 14-Hbeta), 2.54 (3H, s, NCH3), 2.77 (1H, d, J=17.7 Hz, 5-Hbeta), 2.94 (1H, dd, J=16.8, 5.5 Hz, 14-Halpha), 2.95 (1H, dd, J=17.7, 8.1 Hz, 5-Halpha), 3.72 (3H, s, 2-OCH3), 3.77 (3H, s, 10-OCH3), 3.79 (3H, s, 11-OCH3), 3.82 (1H, d, J=8.1 Hz, 6-H), 3.86 (3H, s, 1-OCH3), 4.18 (1H, dq, J=10.7, 7.0 Hz, OCHCH3), 4.25 (1H, dq, J=10.7, 7.0 Hz, OCHCH3), 4.36 (1H, dd, J=5.5, 1.5 Hz, 15-H), 4.51 (1H, dt, J=10.4, 5.5 Hz, 14a-H), 4.80 (1H, br s, OH), 6.46 (1H, s, 9-H); 13C NMR (CDCl3, 125 Hz) delta 8.7 (3 or 12-CH3), 8.8 (3 or 12-CH3), 14.2 (OCH2CH3), 23.5 (C5), 24.8 (C14), 40.3 (NCH3), 50.6 (C9), 52.3 (C14a), 54.6 (C15), 58.5 (C6), 60.1 (2-OCH3), 60.2 (10 or 11-OCH3), 60.3 (10 or 11-OCH3), 60.7 (1-OCH3), 61.7 (OCH2CH3), 114.7 (C4a), 115.3 (C9a), 117.5 (C3 or C12), 117.7 (C3 or C12), 121.8 (C13a), 122.9 (C15a), 143.8 (C10), 144.4 (C1), 146.9 (C13), 148.3 (C4), 149.3 (C2), 149.6 (C11), 169.9 (C7), 171.3 (C16); EIMS m/z 556 (M+, 20), 484 (10), 234 (100); HREIMS m/z 556.2421 (M+, calcd for C29H36N2O9, 556.2421). Anal. Calcd for C29H36N2O9: C, 62.58; H, 6.52; N, 5.03. Found: C, 62.79; H, 6.68; N, 4.98.

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

Reference:
Article; Yokoya, Masashi; Shinada-Fujino, Kimiko; Yoshida, Saiko; Mimura, Masahiro; Takada, Hiroki; Saito, Naoki; Tetrahedron; vol. 68; 22; (2012); p. 4166 – 4181;,
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Application of 849758-12-9, 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. 849758-12-9, name is Methyl 4-bromo-3-fluorobenzoate, This compound has unique chemical properties. The synthetic route is as follows.

A mixture of compound 4-bromo-3-fluoro-benzoic acid methyl ester (1 g, 4.29 mmol), hydrazine hydrate (2.2 ml_, 42.9 mmol) and MeOH (20 ml_) was heated at 70 C for overnight. Concentrated, diluted with EtOAc (300 ml_) and washed with water (100 mL). The organic layer was dried over Na2SO4, filtered and concentrated give the desired product 2AR (0.9 g, 90%).

The chemical industry reduces the impact on the environment during synthesis Methyl 4-bromo-3-fluorobenzoate. I believe this compound will play a more active role in future production and life.

Reference:
Patent; SCHERING CORPORATION; WO2008/156739; (2008); A1;,
Ester – Wikipedia,
Ester – an overview | ScienceDirect Topics