Category: 1459-96-7

Application of 1459-96-7, These common heterocyclic compound, 1459-96-7, name is Dimethyl bicyclo[2.2.2]octane-1,4-dicarboxylate, 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 81 Bicyclo-[2.2.2]octane-1,4-dicarboxylic acid monomethyl ester (IV) A mixture of Bicyclo[2.2.2]octane-1,4-dicarboxylic acid dimethyl ester (III, Example 80, 20.4 g, 89.5 mmol), barium hydroxide octahydrate (14 g, 44.7 mmol) in methanol (160 ml) and water (40 ml) is stirred at 20-25 C. for 18 hour. The mixture is diluted with water (600 ml) and extracted with hexane (150 ml*2). The aqueous mixture is acidified (6 N hydrochloric acid) to pH=1-2 and extracted with chloroform (150 ml*2). The combined chloroform extracts are concentrated. The residue is dissolved in toluene, filtered and concentrated to give the title compound, mp=169-173 C.

The synthetic route of 1459-96-7 has been constantly updated, and we look forward to future research findings.

Reference:
Patent; Biogen, Inc.; US6649600; (2003); B1;,
Ester – Wikipedia,
Ester – an overview | ScienceDirect Topics

Related Products of 1459-96-7,Some common heterocyclic compound, 1459-96-7, name is Dimethyl bicyclo[2.2.2]octane-1,4-dicarboxylate, molecular formula is C12H18O4, 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.

At atmospheric conditions, 0.25g of the Ru-TRIPHOS catalyst ruthenium 1 ,1 ,1 -tris(diphenylphosphinomethyl)ethane, 25 mg of p-toluenesulfonic acid, 2.5g of dimethyl bicyclo[2.2.2]octane-1 ,4-dicarboxylate and 50 imL of p-xylene were added to a 100 imL autoclave reactor. The reactor was then purged three times by pressurizing with nitrogen to 200 psig, then venting the pressure to atmospheric each time. The reactor was then purged three times by pressurizing with hydrogen to approximately 300 psig, then venting the pressure to atmospheric each time. Agitation at 800 rpm was then commenced, and hydrogen was then added to bring the pressure to 1600 psig. The temperature was then increased to 200 C while allowing pressure to rise. After the temperature reaches 200 C, the hydrogen pressure was increased to 2000 psig. These conditions (200 C and 2000 psig) were held for 24 hours of reaction. After 24 hours of reaction, the agitation was stopped, and the heat turned off to let the autoclave start cooling. After cooling to room temperature, pressure was released, and the contents were purged with nitrogen gas and vented. The solution was finally discharged from the autoclave and analyzed by GC-MS and 1H NMR. The conversion of dimethyl bicyclo[2.2.2]octane-1 ,4-dicarboxylate is 30% and the only product methyl 4-(hydroxymethyl)bicyclo[2.2.2]octane-1 -carboxylate (100% selectivity).

These compound has a wide range of applications. It is believed that with the continuous development of the source of the synthetic route Dimethyl bicyclo[2.2.2]octane-1,4-dicarboxylate, its application will become more common.

Reference:
Patent; EASTMAN CHEMICAL COMPANY; HU, Yue, Rachel; HEMBRE, Robert, Thomas; TUSTIN, Gerald, Charles; LIU, Zhufang; ADAMS, Steven, J.; CLARKSON, Jasper, Randle; (59 pag.)WO2019/75004; (2019); A1;,
Ester – Wikipedia,
Ester – an overview | ScienceDirect Topics

Electric Literature of 1459-96-7,Some common heterocyclic compound, 1459-96-7, name is Dimethyl bicyclo[2.2.2]octane-1,4-dicarboxylate, molecular formula is C12H18O4, 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.

At atmospheric conditions, 0.1 g of the Milstein catalyst precursor [2-(Di-tert- butylphosphinomethyl)-6- (0259) (diethylaminomethyl)pyridine]carbonylchlorohydridoruthenium(ll), 30 mg of potassium hydroxide, 2.5g of dimethyl bicyclo[2.2.2]octane-1 ,4-dicarboxylate and 50 imL of p- xylene were added to a 100 imL autoclave reactor. The reactor was then purged three times by pressurizing with nitrogen to 200 psig, then venting the pressure to atmospheric each time. The reactor was then purged three times by pressurizing with hydrogen to approximately 300 psig, then venting the pressure to atmospheric each time. Agitation at 800 rpm was then commenced, and hydrogen was then added to bring the pressure to 750 psig. The temperature was then increased to 140 C while allowing pressure to rise. After the temperature reaches 140 C, the hydrogen pressure was increased to 1000 psig. These conditions (140 C and 1000 psig) were held for 8 hours of reaction. After 8 hours of reaction, the agitation was stopped and the heat turned off to let the autoclave start cooling. After cooling to room temperature, pressure was released, and the contents were purged with nitrogen gas and vented. The solution was finally discharged from the autoclave and analyzed by GC-MS and 1H NMR. The conversion of dimethyl bicyclo[2.2.2]octane-1 ,4-dicarboxylate is 94%; the selectivity of bicyclo[2.2.2]octane-1 ,4-diyldimethanol is 93%; and the selectivity of methyl 4-(hydroxymethyl)bicyclo[2.2.2]octane-1 -carboxylate is 7%.

The synthetic route of 1459-96-7 has been constantly updated, and we look forward to future research findings.

Reference:
Patent; EASTMAN CHEMICAL COMPANY; HU, Yue, Rachel; HEMBRE, Robert, Thomas; TUSTIN, Gerald, Charles; LIU, Zhufang; ADAMS, Steven, J.; CLARKSON, Jasper, Randle; (59 pag.)WO2019/75004; (2019); A1;,
Ester – Wikipedia,
Ester – an overview | ScienceDirect Topics

Reference of 1459-96-7, 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. 1459-96-7 name is Dimethyl bicyclo[2.2.2]octane-1,4-dicarboxylate, 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 A51A: 4-(Methoxycarbonyl)bicyclo[2.2.2]octane-1-carboxylic acid To a solution of dimethyl bicyclo[2.2.2]octane-1,4-dicarboxylate (0.92 g, 4.07 mmol) in MeOH (5 mL) was added LiOH (0.102 g, 4.27 mmol) in water (4 mL) at RT. The reaction mixture was heated at 65 C. for 6 h. It was then cooled to RT and concentrated. The residue was acidified with 1N HCl to pH ?2. The solid (presumed side product diacid) was removed by filtration. The filtrate was extracted with EtOAc, and the combined organic layer was washed with brine, dried over Na2SO4, and filtered. The filtrate was concentrated to afford Intermediate A51A as a white solid, which was used for the next step without further purification. MS(ES): m/z=213 [M+H]+; 1H NMR (400 MHz, DMSO-d6) delta ppm 12.11 (s, 1H), 3.66 (s, 3H), 1.78-1.58 (m, 1H).

At the same time, in my other blogs, there are other synthetic methods of this type of compound, Dimethyl bicyclo[2.2.2]octane-1,4-dicarboxylate, and friends who are interested can also refer to it.

Reference:
Patent; Bristol-Myers Squibb Company; Velaparthi, Upender; Darne, Chetan Padmakar; Liu, Peiying; Wittman, Mark D.; Pearce, Bradley C.; Araujo, Erika M. V.; Dasgupta, Bireshwar; Nair, Jalathi Surendran; Janakiraman, Sakthi Kumaran; Rachamreddy, Chandrasekhar Reddy; Rao, Mettu Mallikarjuna; Karuppiah, Arul Mozhi Selvan Subbiah; Reddy, Bandreddy Subba; Nagalakshmi, Pulicharla; Bora, Rajesh Onkardas; Maheshwarappa, Shilpa Holehatti; Kumaravel, Selvakumar; Mullick, Dibakar; Sistla, Ramesh; (353 pag.)US9273058; (2016); B2;,
Ester – Wikipedia,
Ester – an overview | ScienceDirect Topics

Application of 1459-96-7, 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 1459-96-7 as follows.

A solution of dimethyl bicyclo[2.2.2]octane-l,4-dicarboxylate (58.0 g, 0.25 mol) in methanol (600 mL) was heated under reflux. To this solution was added a solution of potassium hydroxide (9.8 g, 0.175 mol) in methanol (100 mL) and water (12 mL) over 30 minutes. The reaction mixture was refluxed for 24 h. The solvent was then removed and the residue was diluted with water. The aqueous solution was extracted with ethyl acetate (2 x200 mL) to recover starting material (22.0 g), and the aqueous layer was acidified to pH 3 by addition of hydrochloric acid. A precipitate was formed and extracted with ethyl acetate (3 x 300 mL). The combined extracted were washed with brine, dried over sodium sulfate and concentrated to give the titled product (30.0 g, 0.14 mol, 55 % yield).1H NMR(400 MHz, CDCI3) delta ppm 3.65 (s, 3H), 1.81 (s. 12H); MS (ESI) m/z 211.3 [M-H]”.

According to the analysis of related databases, 1459-96-7, the application of this compound in the production field has become more and more popular.

Reference:
Patent; SIGNAL PHARMACEUTICALS, LLC; BENNETT, Brydon, L.; ELSNER, Jan; ERDMAN, Paul; HILGRAF, Robert; LEBRUN, Laurie, Ann; MCCARRICK, Meg; MOGHADDAM, Mehran, F.; NAGY, Mark, A.; NORRIS, Stephen; PAISNER, David, A.; SLOSS, Marianne; ROMANOW, William, J.; SATOH, Yoshitaka; TIKHE, Jayashree; YOON, Won, Hyung; DELGADO, Mercedes; WO2012/145569; (2012); A1;,
Ester – Wikipedia,
Ester – an overview | ScienceDirect Topics

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. 1459-96-7, name is Dimethyl bicyclo[2.2.2]octane-1,4-dicarboxylate, This compound has unique chemical properties. The synthetic route is as follows., 1459-96-7

To the stirred solution of dimethyl bicycle [2.2.2] octane-1, 4-dicarboxylate (6.35 g, 28.1 mmol) in MeOH (60 mL) and Water (12 mL) was added barium hydroxide octahydrate (4.43 g, 14.03 mmol) and the reaction mixture was stirred at room temperature for 12 h. The reaction mixture was diluted with water (150 mL) and extracted with hexane (2 x 100 mL). The aqueous layer was acidified with 1.5 N HC1 and extracted with EtOAc (2 x 200 mL). The organic layer was dried over Na2S04and concentrated under reduced pressure. The residue was stirred with toluene (100 mL) and filtered. The filtrate was concentrated under reduced pressure to yield 4-(methoxycarbonyl) bicycle [2.2.2] octane- 1 -carboxylic acid (3.5 g, 16.49 mmol, 58.8 % yield) as white solid.

If you are interested in these compounds, you can also browse my other articles.Thank you for taking the time to read this article. I hope you enjoyed it.

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

1459-96-7, A common compound: 1459-96-7, name is Dimethyl bicyclo[2.2.2]octane-1,4-dicarboxylate, belongs to esters-buliding-blocks compound, it can change the direction of chemical reaction, and react with certain compounds to generate new functional products. A new synthetic method of this compound is introduced below.

Step C. A mixture of the title compound from Step B above (20 g) and KOH (5.5 g) in MeOH/H2O (10:1, 106 mL) was heated to reflux overnight, cooled to room temperature and concentrated. The residue was diluted with EtOAc and extracted with IN aqueous NaOH (2 x 10O mL). The organic phase was dried (MgSO4), filtered and concentrated to give the starting material as a white solid. The combined aqueous phases were adjusted with 2N aqueous HCl to pH 1-2 and extracted with EtOAc (4 x 250 mL). The combined turbid organic phases were filtered through a fluted filter, washed with saturated aqueous NaCl, dried (MgSO4), filtered and concentrated to give the title compound as a colorless solid (13.1 g, 70%). [MH]+ = 213.

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, Dimethyl bicyclo[2.2.2]octane-1,4-dicarboxylate, other downstream synthetic routes, hurry up and to see.

Reference:
Patent; ALANTOS PHARMACEUTICALS HOLDING, INC.; WO2008/63671; (2008); A2;,
Ester – Wikipedia,
Ester – an overview | ScienceDirect Topics