Month: May 2021

Application of 18014-00-1, These common heterocyclic compound, 18014-00-1, name is Dimethyl 2,5-dibromoterephthalate, 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.

210 mg of 4-chlorothiophene boric acid,151 mg of dimethyl 2,5-dibromobenzene-1,4-dicarboxylate,116mg PdCl2(PPh3)2, 434.7mg saturated K2CO3 aqueous solution was placed in a two-port bottle,Add 12 mL of tetrahydrofuran,The mixture was heated and stirred under reflux for 9 hours under argon.After cooling to room temperature, it was extracted with 30 mL of ethyl acetate.The combined organic layers were washed with saturated brine andNa2SO4 is dry.The solution was then filtered and the solvent removed to give a crude material which was crystallised from ethanol.The product was obtained as a yellow solid.

Statistics shows that Dimethyl 2,5-dibromoterephthalate is playing an increasingly important role. we look forward to future research findings about 18014-00-1.

Reference:
Patent; Lanzhou University; Zhang Haoli; Liu Duanwu; Lin Zewei; Xu Zhuguo; Shi Zifa; (13 pag.)CN109678877; (2019); A;,
Ester – Wikipedia,
Ester – an overview | ScienceDirect Topics

Electric Literature of 6942-39-8, 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. 6942-39-8 name is Methyl 2-bromo-5-fluorobenzoate, 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.

b)4′-Chloro-4-fluoro-3′-[[(tricyclo[3.3.1.13’7]dec-l-ylmethyl)amino]carbonyl]-[l,l’-biphenyI]-2-carboxylic acid, methyl ester[4-Chloro-3-[[(tricyclo[3.3.1.13>7]dec-l-ylmethyl)amino]carbonyl]phenyl]-boronic acid(Example 2 (a)) (200 mg), 2-bromo-5-fluoro-benzoic acid, methyl ester (Example 51 (a))(170 mg), tetrahydrofuran (2 mL), a solution of potassium carbonate (166 mg) in water (1mL) and fe(triphenylphosphine)palladium(II) chloride (20 mg) were placed in a 10 mLmicrowave vial. The mixture was heated to 70 C for 1 hour in a microwave thenevaporated. The residue was partitioned between dichloromethane (20 mL) and water (20mL). The layers were separated and the aqueous was extracted with dichloromethane(2×20 mL). The combined organics were dried (MgSCU,), filtered and evaporated.Purification by chromatography (SiOa, 1:4 ethyl acetate :isohexane as eluant) gave the sub- title compound as an oil (79 mg).MS: APCI(+ve) 456/458 (M+H+).

At the same time, in my other blogs, there are other synthetic methods of this type of compound, Methyl 2-bromo-5-fluorobenzoate, and friends who are interested can also refer to it.

Reference:
Patent; ASTRAZENECA AB; WO2006/25783; (2006); A1;,
Ester – Wikipedia,
Ester – an overview | ScienceDirect Topics

Electric Literature of 223519-11-7, 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. 223519-11-7 name is Methyl 3-amino-5-bromo-4-methylbenzoate, 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.

Methyl 3-amino-5-bromo-4-methylbenzoate (1.15 g, 4.62 mmol), triethylamine (1.28 mL, 9.21 mmol) and dichloromethane (20 mL) were added to a 100 mL two-neck flask, then trifluoroacetic anhydride (0.79 mL, 5.6 mmol) was added dropwise at 0C. The reaction mixture was stirred for 1 h at rt. The mixture was concentrated in vacuo to remove solvent. To the residue was added saturated brine (80 mL) and ethyl acetate (80 mL), and the resulting mixture was partitioned. The organic phase was washed with saturated brine (40 mL x 2), dried over anhydrous sodium sulfate, filtered and concentrated in vacuo to give the title compound as a yellow solid (1.5 g, 95%).MS (ES-API, pos. ion) m/z: 341.0 [M + 2]t

At the same time, in my other blogs, there are other synthetic methods of this type of compound, Methyl 3-amino-5-bromo-4-methylbenzoate, and friends who are interested can also refer to it.

Reference:
Patent; SUNSHINE LAKE PHARMA CO., LTD.; YANG, Xinye; HUANG, Changwei; MA, Facheng; ZHANG, Ji; WANG, Xiaojun; ZHANG, Yingjun; (162 pag.)WO2017/36404; (2017); A1;,
Ester – Wikipedia,
Ester – an overview | ScienceDirect Topics

Electric Literature of 10076-48-9, These common heterocyclic compound, 10076-48-9, name is Methyl 2,2-dimethoxypropanoate, 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.

EXAMPLE 5 Methyl 2,2-dimethoxypropionate (66.9 g, 0.45 mol), hydroquinone (0.1 g), quinoline (74.5 g, 0.58 mol) (dried over potassium hydroxide), and acetyl chloride (48.4 g, 0.62 mol) were combined at 5-10 C. in a Fischer-Porter bottle. Powdered potassium hydroxide (0.45 g, 0.008 mol) was added. The reaction mix formed a thick white slurry. The bottle was sealed, stirred with a magnetic stirrer, and placed in a 122 C. oil bath. After three hours the bottle pressure was 19-22 psig. The reaction mixture was diluted with toluene and the quinoline hydrochloride was removed by filtration. The filtrate was concentrated and distilled to give methyl 2-methoxyacrylate (35 g, 68%): bp 35 C. (4 torr). This example demonstrates that methyl 2-methoxyacrylate can be prepared using superatmospheric pressure.

Statistics shows that Methyl 2,2-dimethoxypropanoate is playing an increasingly important role. we look forward to future research findings about 10076-48-9.

Reference:
Patent; Chevron Research Company; US4304928; (1981); A;,
Ester – Wikipedia,
Ester – an overview | ScienceDirect Topics

Electric Literature of 18014-00-1,Some common heterocyclic compound, 18014-00-1, name is Dimethyl 2,5-dibromoterephthalate, molecular formula is C10H8Br2O4, 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.

2.63 g (10 mmol) of octyl (methyl) -aniline-4-boronic acid was dissolved in 30 ml of tetrahydrofuran, Then 2 ml of water was added, 2.12 g (20 mmol) of sodium carbonate, 1.05 g (3 mmol) of dimethyl 2,5-dibromoterephthalate, 120 mg of tetraphenylphosphine palladium, Reaction under nitrogen for 12 hours; After the reaction is completed, Add 20ml of water to extract. Separate the organic phase, The aqueous phase is extracted three times with 20 dichloromethane. The combined organic phase, Drying over anhydrous sodium sulfate. Evaporate the methylene chloride, Column chromatography (petroleum ether: dichloromethane = 5: 1), Obtained as a light yellow solid, As shown in Formula XI.

The synthetic route of 18014-00-1 has been constantly updated, and we look forward to future research findings.

Reference:
Patent; Lanzhou University; Zhang Haoli; Fan Zhiping; Xu Zhuguo; Shi Zifa; (14 pag.)CN105367451; (2017); B;,
Ester – Wikipedia,
Ester – an overview | ScienceDirect Topics

Electric Literature of 1949-51-5, A common heterocyclic compound, 1949-51-5, name is Ethyl 3,5-diaminobenzoate, molecular formula is C9H12N2O2, 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.

In a round-bottom flask placed in an ice bath, 11 (1.0 eq.) was solubilized in a mixture of dioxane and water (2:1), followed by addition of triethylamine (Et3N; 2.2 eq.). Next, di-tert-butyl-dicarbonate ((Boc)2O; 1.0 eq.) was solubilized in a small amount of dioxane and added dropwise to the mixture. The reaction was stirred at room temperature overnight. The solvents were evaporated and the crude was dissolved in ethyl acetate and washed with 10% aqueous solution of citric acid and water. The collected organic phases were dried over MgSO4, concentrated in vacuo and purified by column chromatography (dichloromethane/acetonitrile 95/5-90/10). The desired product formed pale-yellow crystals (80% yield).

The synthetic route of 1949-51-5 has been constantly updated, and we look forward to future research findings.

Reference:
Article; Czescik, Joanna; Zamolo, Susanna; Darbre, Tamis; Mancin, Fabrizio; Scrimin, Paolo; Molecules; vol. 24; 15; (2019);,
Ester – Wikipedia,
Ester – an overview | ScienceDirect Topics

Application of 3195-24-2,Some common heterocyclic compound, 3195-24-2, name is Diethyl 2,2-diallylmalonate, molecular formula is C13H20O4, 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.

A study of the RC of several substrates has also been carried out. Reactions were run in toluene at 80C in the presence of 1 to 5 mol% of cis-2, the higher catalyst loading being only necessary for the formation 17 featuring a tetra-substituted double bond (Table 4 below, entry 3). The RCM of unhindered malonate derivatives was achieved in short reaction times (less than 1 hour) and in good yields. Indeed, di- and tri-substituted cyclopentenes 15 and 9 were obtained in quantitative yields (entries 1 & 2). Nevertheless, highly constrained substrate 16 could not be cyclized with full conversion, even after 24h at 80C, and was isolated in 70% yield (entry 3). Finally, 6- and 7-membered rings 19 and 21 were obtained in respectively 96 and 87% yield, and no increase in reaction time compared to 5-membered ring 15 (entries 4 & 5). Of note, a dilution to 0.05M was necessary to obtain 21 without observing parallel formation of polymers. We next attempted the RCM of cyano analogues 24 and 26 (entries 6 & 7). Non-hindered cyclopentene 23 was isolated in good yield (88%), indicating that the presence of potentially chelating cyano groups was not detrimental to catalysis. Nevertheless, cis-2 was unable to promote the formation of 25, the starting material remaining unreacted. Tosylamine-based olefins were next investigated. The cyclization of these compounds was found very efficient regardless of hindrance and ring size. Indeed, 5-, 6- and 7-membered compounds 7, 27 and 29 were isolated in excellent yields (entries 8-10), albeit a slight increase in reaction time was needed for larger rings. Catalyst loading of only 2 mol% was necessary to achieve the cyclizations of 30 and 32 to obtain tetrasubstituted 5- and 6-membered rings 31 and 33 in good yields (entries 11 & 12), even so 5 hours of reaction were needed for dihydropyrrole 31. Amide and ether-based substrates were also efficiently cyclized, with yields spanning from 80% to 99% (entries 13-17). Increasing the ring size to 6 or 7 members was not detrimental, as products 39, 41 and 43 were obtained excellent yields in less than 1 hour (entries 15-17). From this study, catalyst c/s-2 seemed to be highly tolerant to functionalities and able to effect RCM easily.This utility of the complexes of the invention is illustrated further in figure 4 which shows RCM of compound 30 (table 4 entry 11 ) in toluene at 80C carried out with a range of Ru complexes. Trans or cis-2 both rapidly produce a high conversion whereas prior art complexes Hov-ll, G-ll, M2 (structures shown in Scheme 1 ) and M31 (which is the pyridine complex 1 in scheme 2) did not produce any better than about 60% conversion (complex M2) under these conditions

The synthetic route of 3195-24-2 has been constantly updated, and we look forward to future research findings.

Reference:
Patent; UNIVERSITY COURT OF THE UNIVERSITY OF ST ANDREWS; CAZIN, Catherine; WO2011/117571; (2011); A1;,
Ester – Wikipedia,
Ester – an overview | ScienceDirect Topics

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 1070-64-0 as follows. Formula: C10H18Cl2O2

To a solution of ethyl 6,8-dichlorooctanoate (6.01 g, 25 mmol) in 95% ethanol (10mL)was added sodium hydroxide (2 g, 50 mmol) and water (38 mL). The mixture was heated to 50 C for 1.5 h and the aqueous disodium diselenide (prepared from 3.95 g selenium powder19) was then added dropwise at 65 C. After stirring for 2 h, the mixture was cooled to 40 C and activated carbon (8 g) was then added. After stirring for 0.5 h, the mixture was filtered, and the ethanol was distilled off under reduced pressure (caution: the temperatureof the filtrate must not exceed 50C). Water (400 mL) was added to the residue and the mixture was cooled to 0 C. A solution of 10% hydrochloric acid was then added dropwise till pH = 1, resulting in the formation of a solid product. The solid was filtered and washed thoroughly with water.

According to the analysis of related databases, 1070-64-0, the application of this compound in the production field has become more and more popular.

Reference:
Article; Xu, Feng; Yang, Zhen-Zhen; Zhang, Shi-Jie; Phosphorus, Sulfur and Silicon and the Related Elements; vol. 188; 10; (2013); p. 1312 – 1319;,
Ester – Wikipedia,
Ester – an overview | ScienceDirect Topics

Application of 14062-29-4, The chemical industry reduces the impact on the environment during synthesis 14062-29-4, name is Ethyl 2-(3-chlorophenyl)acetate, I believe this compound will play a more active role in future production and life.

EXAMPLE 23 6-(3-Chlorobenzyl)-1-(2-methoxyphenyl)-1,5-dihydro-4H-pyrazolo[3,4-d]pyrimidin-4-one In analogy to the preparation of Example 9, 180 mg (76% of theory) of the desired product are obtained as a colourless solid starting from 0.15 g (0.65 mmol) of 5-amino-1-(2-methoxyphenyl)-1H-pyrazole-4-carboxamide (Example 31A), 0.394 g (98% purity, 1.94 mmol) of ethyl (3-chlorophenyl)acetate and 0.129 g (3.23 mmol) of 60% sodium hydride. m.p.: 196 C. MS (ESI pos): m/z=367 (M+H)+ 1H-NMR (300 MHz, DMSO-d6): delta=3.7 (s, 3H), 3.9 (s, 2H), 7.0-7.6 (m, 8H), 8.2 (s, 1H), 12.4 (s, 1H) ppm.

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-chlorophenyl)acetate, other downstream synthetic routes, hurry up and to see.

Reference:
Patent; Bayer HealthCare AG; US2007/161662; (2007); A1;,
Ester – Wikipedia,
Ester – an overview | ScienceDirect Topics

Synthetic Route of 2969-81-5, 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. 2969-81-5, name is Ethyl 4-bromobutyrate, This compound has unique chemical properties. The synthetic route is as follows.

To a solution of 4-chlorophenol (10 g, 77.784 mmol, 1 equiv) in N,N- dimethylformamide (100 mL) was added anhydrous potassium carbonate (21 .5 g, 1 16.6 mmol, 2 equiv) and ethyl 4-bromobutanoate (16.7 mL, 1 16.677 mmol, 1 .5 equiv). The reaction mixture was heated to 140 C and stirred for 4 h. The progress of the reaction was monitored by TLC. After completion of reaction, the reaction mixture was allowed to cool to 27 C, filtered the solid and washed with ethyl acetate (700 mL). The filtrate was washed with water (2 x 200 mL), brine solution (100 mL), dried over anhydrous sodium sulphate, filtered and concentrated under reduced pressure to give the crude product. The crude product was purified by silica gel column chromatography using 10 % ethyl acetate in hexane as eluent to obtain ethyl 4-(4-chlorophenoxy)butanoate (17.0 g, 89 % yield) as white solid. LCMS (ES) m/z = 243.1 [M+H]+. NMR (400 MHz, CDCI3): delta ppm 1 .25 (t, J = 7.2 Hz, 3 H), 2.06 – 2.12 (m, 2 H), 2.49 (t, J = 7.6 Hz, 2 H), 3.97 (t, J = 6.0 Hz, 2 H), 4.1 1 – 4.17 (m, 2 H), 6.80 (d, J = 8.8 Hz, 2 H), 7.21 (d, J = 8.8 Hz, 2 H).

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

Reference:
Patent; GLAXOSMITHKLINE INTELLECTUAL PROPERTY DEVELOPMENT LIMITED; AXTEN, Jeffrey; CHEUNG, Mui; DEAN, Anthony W.; DEMARTINO, Michael P.; EIDAM, Hilary Schenck; KETHIRI, Raghava Reddy; KALITA, Biswajil; KRISTAM, Rajendra; (162 pag.)WO2017/212423; (2017); A1;,
Ester – Wikipedia,
Ester – an overview | ScienceDirect Topics