Category: 145576-28-9

145576-28-9, name is Ethyl 4-methylenecyclohexanecarboxylate, belongs to esters-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. category: esters-buliding-blocks

Preparation of 4-Methoxy-4-methylcyclohexanecarboxylic acid; A suspension of Hg(OAc)2 (2.2 g, 6.96 mmol) in dry methanol (15 mL) was cooled to O0C under stirring, 4-Methylenecyclohexanecarboxylic acid ethyl ester (0.9 g, 5.36 mmol) was added and maintained for 15 min. To the resulted reaction mixture, 3M NaOH (12 mL) was added followed by the addition of a mixture of NaBH4 solution in 3M NaOH solution (12 mL) and maintained for 10 min. The reaction mixture was allowed to rt and maintained for 1h additionally. The reaction mass was filtered through celite bed, the filtrate was cooled, acidified and then was extracted with DCM (100 mL). The organic layer was washed with water (2 x 50 mL), brine solution (50 mL), dried over anhydrous sodium sulfate and concentrated to obtain the crude product. The crude was purified by column chromatography over silica gel column using 10% EtOAc in pet ether as eluting solvent to obtain the pure product (2) as liquid (500 mg, 55%). 1HNMR(CDCl3)-. delta 3.22(s, 1H), 3.15(s, 3H), 2.18-2.36(m, 1H), 1.9(d, 2H)1 1.5-1.82(m, 5H), 1.2-1.32(m, 2H) and 1.1 (s, 3H). Mass: (M-1) 171 calculated for C9H15O3.

The synthetic route of 145576-28-9 has been constantly updated, and we look forward to future research findings.

Reference:
Patent; PFIZER PRODUCTS INC.; WO2008/84300; (2008); A1;,
Ester – Wikipedia,
Ester – an overview | ScienceDirect Topics

Adding a certain compound to certain chemical reactions, such as: 145576-28-9, name is Ethyl 4-methylenecyclohexanecarboxylate, belongs to esters-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 145576-28-9, COA of Formula: C10H16O2

General procedure: The alkene (1.16 mmol, 1 equivalent) was dissolved in a vigorously stirred mixture of DCM (7 mL) and acetonitrile (7 mL) under nitrogen. 2,6-Lutidine (0.27 mL, 2.32 mmol, 2 equivalents), water (10.5 mL) and sodium periodate (993 mg, 4.64 mmol, 4 equivalents) were then added sequentially. The reaction concentration with respect to the alkene was 0.047 M in a mixture of 1: 1: 1.5 – DCM: acetonitrile: water. To the resulting mixture a stock solution of ruthenium(III) chloride trihydrate (0.035 M in water) (1.16 mL, 0.04 mmol, 3.5 mol %) was added dropwise via a syringe forming a brown suspension. The reaction was stirred vigorously at 20 C for 1 h (or for the time indicated in the Tables 2 and 3). The reaction was diluted with water (20 mL) then extracted with DCM (3 x 20 mL). The organic extracts were combined then washed with brine (20 mL), passed through a phase separating cartridge and the volatiles were removed under reduced pressure. The resulting residue was purified by flash silica chromatography (EtOAc / heptane) to afford the ketone.

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Reference:
Article; Watson, David W.; Gill, Matthew; Kemmitt, Paul; Lamont, Scott G.; Popescu, Mihai V.; Simpson, Iain; Tetrahedron Letters; vol. 59; 51; (2018); p. 4479 – 4482;,
Ester – Wikipedia,
Ester – an overview | ScienceDirect Topics

These common heterocyclic compound, 145576-28-9, name is Ethyl 4-methylenecyclohexanecarboxylate, 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. Application In Synthesis of Ethyl 4-methylenecyclohexanecarboxylate

Ethyl 4-methylidenecyclohexanecarboxylate (50 mg, 0.3 mmol) was stirred with 0.5M 9-borabicyclo[3.3.1]nonane in THF (0.89 mL), which was added slowly undernitrogen. The reaction mixture was stirred at room temperature overnight. The crude mixture was cooled to 0C and Intermediate 29 (203 mg, 0.51 mmol) in DMF (3 mL) was added, followed by bis[3 -(diphenylphosphanyl)cyclopenta-2,4-dien- 1 -yl] iron dichloropalladium dichloromethane complex (24 mg, 0.03 mmol) and 2M aqueous potassium carbonate solution (0.22 mL). The reaction mixture was stirred at room temperature overthe weekend, then heated at 60C for 1.5 h. Further bis[3-(diphenylphosphanyl)- cyclopenta-2,4-dien- 1 -yl]iron dichloropalladium dichloromethane complex (50 mg, 0.061 mmol) was added and the mixture was heated at 80C overnight under nitrogen. The reaction mixture was added to cold water and 0.5M aqueous NaOH solution (0.5 mL) was added. The mixture was extracted with DCM (100 mL), dried over sodium sulphate,filtered and concentrated under vacuum. The resulting brown oil was purified twice by FCC, eluting with 0-30% MeOH in DCM. The material was further purified by preparative HPLC (Method C), to afford the title compound (11.4 mg, 7%) as a brown oil. Method B HPLC-MS: MH+ m/z 535, RT 1.72 minutes.

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

Reference:
Patent; UCB PHARMA S.A.; BENTLEY, Jonathan Mark; BROOKINGS, Daniel Christopher; BROWN, Julien Alistair; CAIN, Thomas Paul; CHOVATIA, Praful Tulshi; FOLEY, Anne Marie; GALLIMORE, Ellen Olivia; GLEAVE, Laura Jane; HEIFETZ, Alexander; HORSLEY, Helen Tracey; HUTCHINGS, Martin Clive; JACKSON, Victoria Elizabeth; JOHNSON, James Andrew; JOHNSTONE, Craig; KROEPLIEN, Boris; LECOMTE, Fabien Claude; LEIGH, Deborah; LOWE, Martin Alexander; MADDEN, James; PORTER, John Robert; QUINCEY, Joanna Rachel; REED, Laura Claire; REUBERSON, James Thomas; RICHARDSON, Anthony John; RICHARDSON, Sarah Emily; SELBY, Matthew Duncan; SHAW, Michael Alan; ZHU, Zhaoning; WO2014/9295; (2014); A1;,
Ester – Wikipedia,
Ester – an overview | ScienceDirect Topics

Application of 145576-28-9, 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 145576-28-9 as follows.

To a solution of dry dicyclohexylamine (0.777 mL, 3.90 mmol) in toluene (20 mL) in a round-bottom flask at 0 C. under Ar was added n-butyllithium (2.44 mL, 3.90 mmol) slowly. The reaction was stirred at 0 C. for 30 min. To this prepared lithium dicyclohexylamide solution was added ethyl 4-methylenecyclohexanecarboxylate (555 mg, 3.30 mmol) in toluene (1 mL) slowly over a period of 5 min. The reaction mixture was stirred at 0 C. for additional 30 min to generate the lithium enolate. In a 5 mL pear-shaped flask was placed di-p-bromobis(tri-tert-butylphosphino)dipalladium (I) (1.2 mg, 1.5 mumol) and the flask was capped with a rubber septum. Argon gas was flushed through the flask for 10 min. 1-Bromo-3-phenoxybenzene (747 mg, 3 mmol) in toluene (1 mL) was then added. The resulting solution was transferred via cannula into the round-bottom flask containing the 0 C. THF solution of the lithium enolate of the ethyl ester. Additional toluene (2×0.5 mL) was added to the pear-shaped flask, and this solution was also transferred into the round-bottom flask by cannula. The reaction mixture was allowed to warm to rt and stirred at rt for 3 days. The reaction was quenched with saturated aq. NH4Cl and diluted with EtOAc. The organic layer was washed with water and brine, dried over MgSO4, filtered, and concentrated in vacuo. The residue was purified by preparative HPLC (PHENOMENEX Axia 5mu C18 30×100 mm column; detection at 220 nm; flow rate=40 mL/min; continuous gradient from 30% B to 100% B over 10 min+2 min hold time at 100% B, where A=90:10:0.1 H2O:MeOH:TFA and B=90:10:0.1 MeOH:H2O:TFA) to afford the title compound (221 mg, 22% yield) as a colorless oil. LCMS, [M+H]+=337.1. 1H NMR (500 MHz, CDCl3) delta 7.38-7.33 (m, 2H), 7.33-7.27 (m, 1H), 7.19-7.10 (m, 3H), 7.04-6.99 (m, 2H), 6.89 (ddd, J=8.0, 2.4, 0.8 Hz, 1H), 4.68 (s, 2H), 4.17 (q, J=7.2 Hz, 2H), 2.61-2.53 (m, 2H), 2.36-2.21 (m, 4H), 1.88-1.79 (m, 2H), 1.22 (t, J=7.0 Hz, 3H).

According to the analysis of related databases, 145576-28-9, the application of this compound in the production field has become more and more popular.

Reference:
Patent; Zhang, Hao; Cheng, Peter T.W.; Chen, Sean; Tao, Shiwei; Wu, Shung C.; Negash, Lidet A.; US2014/275173; (2014); A1;,
Ester – Wikipedia,
Ester – an overview | ScienceDirect Topics

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. 145576-28-9, name is Ethyl 4-methylenecyclohexanecarboxylate, A new synthetic method of this compound is introduced below., COA of Formula: C10H16O2

At 0 C, to a solution of ethyl 4-methylenecyclohexanecarboxylate (0.08 g) in DCE (1 mL) was added chloroiodomethane (0.110 mL, 1.522 mmol), followed bythe addition of 1 N diethylzinc in hexane (0.76 1 mL, 0.76 1 mmol). The reaction was stirred at 0 C for 1 hr, then stirred at rt for 18 hrs. The reaction mixture was diluted with EtOAc and 1 N HC1, the organic phase was washed with sat. NaC1, dried over anhydrous Na2SO4, filtered and concentrated. The crude product was charged to a 25 g silica gel cartridge which was eluted with a 20 mm gradient of 0-6% EtOAc inhexane to yield ethyl spiro[2.5]octane-6-carboxylate. ?H NMR (400 MHz, CDC13) ppm 4.08-4.18(2 H, m), 2.32 (1 H, tq, J=11.01, 3.53 Hz), 1.85 – 1.93 (2 H, m), 1.53- 1.74 (4 H, m), 1.28 – 1.35 (2 H, m), 1.22 – 1.28 (3 H, m), 0.28 (2 H, ddd, J=8.53, 5.52, 1.51 Hz), 0.17 – 0.25 (2 H, m).

The basis of chemical reaction formula synthesis, the synthesis route is composed of some specific reactions and combined according to certain logical thinking. We look forward to the emergence of more reaction modes in the future.

Reference:
Patent; BRISTOL-MYERS SQUIBB COMPANY; HEWAWASAM, Piyasena; LOPEZ, Omar D.; TU, Yong; WANG, Alan Xiangdong; XU, Ningning; KADOW, John F.; MEANWELL, Nicholas A.; GUPTA, Samayamunthula Venkata Satya Arun Kumar; KUMAR, Indasi J. Gopi; PUNUGUPATI, Suresh Kumar; BELEMA, Makonen; WO2015/5901; (2015); A1;,
Ester – Wikipedia,
Ester – an overview | ScienceDirect Topics

Related Products of 145576-28-9, 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. 145576-28-9, name is Ethyl 4-methylenecyclohexanecarboxylate belongs to esters-buliding-blocks compound, it is a common compound, a new synthetic route is introduced below.

To a solution of ethyl 4-methylenecyclohexanecarboxylate (0.15 g, 0.892 mmol) in diglyme (3 mL) was added a solution of sodium 2-chloro-2,2- difluoroacetate (0.544 g, 3.57 mmol) in 5 ml of diglyme via syringe pump at 0.5 ml/h at 150 C. The reaction was cooled to rt, then diluted with DCM and washed with water, brine, dried over Na2SO4, filtered and concentrated. The residue was chargedto a 40 g silica gel cartridge which was eluted with a 20 mm gradient of 0-20% EtOAc in hexane to yield ethyl 1,1-difluorospiro[2.5]octane-6-carboxylate. ?H NMR (400 MHz, CDC13) ppm 4.09 – 4.19 (2 H, m), 2.29 -2.45 (1 H, m), 1.89 -2.03 (2 H, m), 1.55 – 1.72(5 H, m), 1.45 – 1.54(1 H, m), 1.31 – 1.39 (1 H, m), 1.21 – 1.30(3 H, m), 0.84 – 0.94 (1 H, m).

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 4-methylenecyclohexanecarboxylate, other downstream synthetic routes, hurry up and to see.

Reference:
Patent; BRISTOL-MYERS SQUIBB COMPANY; HEWAWASAM, Piyasena; LOPEZ, Omar D.; TU, Yong; WANG, Alan Xiangdong; XU, Ningning; KADOW, John F.; MEANWELL, Nicholas A.; GUPTA, Samayamunthula Venkata Satya Arun Kumar; KUMAR, Indasi J. Gopi; PUNUGUPATI, Suresh Kumar; BELEMA, Makonen; WO2015/5901; (2015); A1;,
Ester – Wikipedia,
Ester – an overview | ScienceDirect Topics

Application of 145576-28-9, 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. 145576-28-9, name is Ethyl 4-methylenecyclohexanecarboxylate belongs to esters-buliding-blocks compound, it is a common compound, a new synthetic route is introduced below.

Cap N-8 At 0 C., to a solution of ethyl 4-methylenecyclohexanecarboxylate (0.08 g) in DCE (1 mL) was added chloroiodomethane (0.110 mL, 1.522 mmol), followed by the addition of 1 N diethylzinc in hexane (0.761 mL, 0.761 mmol). The reaction was stirred at 0 C. for 1 hr, then stirred at rt for 18 hrs. The reaction mixture was diluted with EtOAc and 1 N HCl, the organic phase was washed with sat. NaCl, dried over anhydrous Na2SO4, filtered and concentrated. The crude product was charged to a 25 g silica gel cartridge which was eluted with a 20 min gradient of 0-6% EtOAc in hexane to yield ethyl spiro[2.5]octane-6-carboxylate. 1H NMR (400 MHz, CDCl3) delta ppm 4.08-4.18 (2H, m), 2.32 (1H, tq, J=11.01, 3.53 Hz), 1.85-1.93 (2H, m), 1.53-1.74 (4H, m), 1.28-1.35 (2H, m), 1.22-1.28 (3H, m), 0.28 (2H, ddd, J=8.53, 5.52, 1.51 Hz), 0.17-0.25 (2H, m).

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

Reference:
Patent; Bristol-Myers Squibb Company; Hewawasam, Piyasena; Kadow, John F.; Lopez, Omar D.; Meanwell, Nicholas A.; Tu, Yong; Wang, Alan Xiangdong; Xu, Ningning; Gupta, Samayamunthula Venkata Satya Arun Kumar; Srinivasu, Pothukanuri; Kumar, Indasi Gopi; Kumar, Ponugupati Suresh; Belema, Makonen; Fridell, Robert A.; Gao, Min; Lemm, Julie A.; O’Boyle, II, Donald R.; Sun, Jin-Hua; Wang, Chunfu; Wang, Ying-Kai; US2013/183269; (2013); A1;,
Ester – Wikipedia,
Ester – an overview | ScienceDirect Topics