Category: 94994-25-9

Related Products of 94994-25-9, A common heterocyclic compound, 94994-25-9, name is Methyl 4-formylbicyclo[2.2.2]octane-1-carboxylate, molecular formula is C11H16O3, 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.

Intermediate A51M: Methyl 4-(difluoromethyl)bicyclo[2.2.2]octane-1-carboxylate To a solution of Intermediate A51L (400 mg, 2.038 mmol) at 0 C. in CH2Cl2 (8 mL) was added DAST (0.673 mL, 5.10 mmol). The reaction mixture was stirred at RT overnight. The reaction mixture was cooled to 0 C. and carefully quenched with a solution of NaHCO3. The layers were separated. The aqueous layer was extracted with CH2Cl2. The combined organic layer was washed with brine, dried over Na2SO4, and filtered. The filtrate was concentrated. The residue was purified by silica gel chromatography (40 g REDISEP column, eluting with 0-20% EtOAc in hexane). Fractions containing the product were combined and evaporated to afford Intermediate A51M (280 mg, 62.9%). MS(ES): m/z=199 [M+H]+; 1H NMR (400 MHz, chloroform-d) delta ppm 5.54-5.26 (m, 1H), 3.68 (s, 3H), 1.89-1.76 (m, 6H), 1.65-1.50 (m, 6H).

The synthetic route of 94994-25-9 has been constantly updated, and we look forward to future research findings.

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

Related Products of 94994-25-9, A common heterocyclic compound, 94994-25-9, name is Methyl 4-formylbicyclo[2.2.2]octane-1-carboxylate, molecular formula is C11H16O3, 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.

Intermediate A51M: Methyl 4-(difluoromethyl)bicyclo[2.2.2]octane-1-carboxylate To a solution of Intermediate A51L (400 mg, 2.038 mmol) at 0 C. in CH2Cl2 (8 mL) was added DAST (0.673 mL, 5.10 mmol). The reaction mixture was stirred at RT overnight. The reaction mixture was cooled to 0 C. and carefully quenched with a solution of NaHCO3. The layers were separated. The aqueous layer was extracted with CH2Cl2. The combined organic layer was washed with brine, dried over Na2SO4, and filtered. The filtrate was concentrated. The residue was purified by silica gel chromatography (40 g REDISEP column, eluting with 0-20% EtOAc in hexane). Fractions containing the product were combined and evaporated to afford Intermediate A51M (280 mg, 62.9%). MS(ES): m/z=199 [M+H]+; 1H NMR (400 MHz, chloroform-d) delta ppm 5.54-5.26 (m, 1H), 3.68 (s, 3H), 1.89-1.76 (m, 6H), 1.65-1.50 (m, 6H).

The synthetic route of 94994-25-9 has been constantly updated, and we look forward to future research findings.

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

Synthetic Route of 94994-25-9, These common heterocyclic compound, 94994-25-9, name is Methyl 4-formylbicyclo[2.2.2]octane-1-carboxylate, 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 21 4-[4-Benzo[1,3]dioxol-5-yl-5-(6-methyl-pyridin-2-yl)-1H-imidazol-2-yl]-bicyclo[2.2.2]octane-1-carboxylic acid methyl ester 4-Formyl-bicyclo[2.2.2]octane-1-carboxylic acid methyl ester (0.284 g, 1.0 mmol) was added to a solution of 1-benzo[1,3]dioxol-5-yl-2-(6-methyl-pyridin-2-yl)-ethane-1,2-dione 2-oxime (see Example 4; 0.215 g, 1.1 mmol) and ammonium acetate (1.54 g, 20 mmol) in acetic acid (5 mL). The mixture was refluxed for 2 hours. Solvent was removed under reduced pressure. The reaction mixture was then quenched with ammonia/ice mixture. The aqueous solution was extracted with ethyl acetate. Ethyl acetate extract was washed with brine, dried over sodium sulfate, filtered, and concentrated to give 0.300 g (65%) of the hydroxyimidazole as a yellow solid. MS (ESP+) m/z 462.3 (M+1).

Statistics shows that Methyl 4-formylbicyclo[2.2.2]octane-1-carboxylate is playing an increasingly important role. we look forward to future research findings about 94994-25-9.

Reference:
Patent; Lee, Wen-Cherng; Sun, Lihong; Shan, Feng; Chuaqui, Claudio; Zheng, Zhongli; Petter, Russell C; US2006/63809; (2006); A1;,
Ester – Wikipedia,
Ester – an overview | ScienceDirect Topics

Application of 94994-25-9, A common heterocyclic compound, 94994-25-9, name is Methyl 4-formylbicyclo[2.2.2]octane-1-carboxylate, molecular formula is C11H16O3, 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 stirred solution of methyltriphenylphosphonium bromide (9.1 g, 12.8 mmol) in THF (50 ml) at 0 C. was added potassium hexamethyldisilazide (0.5M in toluene, 48.6 ml), dropwise over 5 min. The resulting mixture was allowed to warm up to room temperature over 1 h, then cooled again to 0 C. and treated with methyl 4-formylbicyclo[2.2.2]octane-1-carboxylate 15-A (Chapman, N. B. et al. J. Org. Chem., 1970, 35, 917) (2.5 g, 12.8 mmol). The reaction mixture was stirred at room temperature for 18 h then diluted with EtOAc (350 ml). The organic phase was washed with aqueous HCl (1 N), saturated aqueous sodium bicarbonate, and brine, then dried (Na2SO4) and concentrated in vacuo. The resulting solid was purified by flash silica gel chromatography, eluting with a gradient 0-4% EtOAc/hexanes. The resulting methyl 4-vinylbicyclo[2.2.2]octane-1-carboxylate 15-B was isolated as a clear, colorless oil.

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; Waddell, Sherman T.; Santorelli, Gina M.; Maletic, Milana M.; Leeman, Aaron H.; Gu, Xin; Graham, Donald W.; Balkovec, James M.; Aster, Susan D.; US2004/133011; (2004); A1;,
Ester – Wikipedia,
Ester – an overview | ScienceDirect Topics

These common heterocyclic compound, 94994-25-9, name is Methyl 4-formylbicyclo[2.2.2]octane-1-carboxylate, 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. Recommanded Product: Methyl 4-formylbicyclo[2.2.2]octane-1-carboxylate

Step A:(Benzyloxycarbonylmethyl)triphenylphosphonium bromide (4.6 g, 9.4 mmol) wasazeotroped twice from toluene, and then suspended in 30 mL dry THF. Potassium hexamethyldisilazide(0.5 M in toluene, 16.8 mL, 8.4 mmol) was added dropwise at room temperature and the yellow solutionwas allowed to stir for 1 h, after which time it became milky white. A solution of 4-carbomethoxybicyclo[2.2.2] octane-1-carboxaldehyde (2-1) (0.50 g, 2.55 mmol) (Adcock, W., Kok, G. B.J. Ore. Chem. 50: 1079-1087 (1985)) and benzoic acid (0.015 g, 0.13 mmol) in 2 mL of dry THF wasprepared and added dropwise by syringe at room temperature. The mixture was heated to 90 C andallowed to stir at reflux temperature, after which time the mixture was diluted with 200 mL of ethylacetate and washed consecutively with 50 mL portions of 1 N HCI (twice), saturated aq. sodiumbicarbonate, and brine. The organic layer was dried using magnesium sulfate, and the solvent wasremoved under reduced pressure. The residue was chromatographed on silica, eluting with a gradient of5% to 10% ethyl acetate in hexane to provide methyl 4-[(lE)-3-(benzyloxy)-3-oxoprop-l-en-l-yl]bicyclo[2.2.2]octane-l-carboxylate (2-2) as a colorless oil. IH NMR (500 MHz, CDCls): 5 7.4 (5H,m), 6.94 (IH, d, J = 17 Hz), 5.77 (IH, d, J = 17 Hz), 5.21 (2H, s), 3.69 (3H, s), 1.86 (6H, m), 1.63 (6H,m) ppm.

The synthetic route of Methyl 4-formylbicyclo[2.2.2]octane-1-carboxylate has been constantly updated, and we look forward to future research findings.

Reference:
Patent; MERCK & CO., INC.; WO2006/17542; (2006); 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 94994-25-9 as follows. category: esters-buliding-blocks

Method B. 1 (9.81 g, 0.0500 mol) was dissolved in THF (100 mL). Diethyl cyanomethyl- phosphonate (8.90 mL, 0.0550 mol) was added. The mixture was cooled with an ice bath. Sodium tert-butoxide (5.28 g, 0.0550 mol) was added slowly. After 10 min, the suspension became a clear solution. After 2 h, aq NaOH (1M, 50 mL) was added. The mixture was stirred at room temperature overnight. To the reaction mixture was added water (100 mL) and MTBE (100 mL). The aqueous layer was separated and washed with MTBE (100 mL) cooled with ice batch and acidified with HCI (2M, 50 mL). The precipitate was collected by filtration and dried in a vacuum oven at 50 C overnight to yield the product (3) as white solid (7.92 g) in 72.2% yield.

According to the analysis of related databases, 94994-25-9, the application of this compound in the production field has become more and more popular.

Reference:
Patent; BIOGEN IDEC MA INC; KWOK, Daw-long, Albert; KIESMAN, William; HUMORA, Michael; CAI, Xiongwei; LITTKE, Adam; CHANG, HeXi; WO2011/63268; (2011); A2;,
Ester – Wikipedia,
Ester – an overview | ScienceDirect Topics

Related Products of 94994-25-9, These common heterocyclic compound, 94994-25-9, name is Methyl 4-formylbicyclo[2.2.2]octane-1-carboxylate, 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.

[2-(2-Methyl-1,3-dioxolan-2-yl)ethyl](triphenyl)phosphonium bromide (4-A, Synthesis: 532 (1986)) (5.99 g, 12.7 mmol) was stirred in dry THF (200 mL). Potassium bis(trimethylsilyl)amide (20.4 mL, 2M soln in toluene, 10.2 mmol) was added. The reaction was allowed to stir for 30 min. The reaction mixture was then cooled to -78 C. Methyl 4-formylbicyclo[2.2.2]octane-1-carboxylate was added at -78 C. by cannula. The reaction was allowed to warm to room temperature overnight. The volume was reduced by evaporation of THF in vacuo. 100 mL of water was added. The mixture was then layered with 100 mL of diethyl ether. The ether was extracted and dried (MgSO4). The product (methyl 4-[(1E)-3-(2-methyl-1,3-dioxolan-2-yl)prop-1-enyl]bicyclo[2.2.2]octane-1-carboxylate (4-B)) was purified by flash chromatography on silica gel with 10/90 ethyl acetate-hexane mixture.

The synthetic route of 94994-25-9 has been constantly updated, and we look forward to future research findings.

Reference:
Patent; Waddell, Sherman T.; Santorelli, Gina M.; Maletic, Milana M.; Leeman, Aaron H.; Gu, Xin; Graham, Donald W.; Balkovec, James M.; Aster, Susan D.; US2004/133011; (2004); A1;,
Ester – Wikipedia,
Ester – an overview | ScienceDirect Topics

Adding a certain compound to certain chemical reactions, such as: 94994-25-9, name is Methyl 4-formylbicyclo[2.2.2]octane-1-carboxylate, 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 94994-25-9, Recommanded Product: Methyl 4-formylbicyclo[2.2.2]octane-1-carboxylate

Step A:Diethyl (ethylsulfonomethane)phosphonate (1.12 g, 4.6 mmol) (Popoff, I. C. et al. J. Org.Chem. 34: 1128-30 (1969)) and 4-carbomethoxybicyclo[2.2.2] octane-1-carboxaldehyde (1-1) (0.82 g,4.2 mmol) (Adcock, W., Kok, G. B. J. Ore. Chem. 50: 1079-1087 (1985)) were dissolved in 8 mL ofabsolute methanol. The mixture was placed under nitrogen atmosphere, cooled in an ice-bath, andtreated with 0.5M solution of sodium methoxide in methanol (8.8 mL, 4.4 mmol). The reaction mixturewas kept under reflux for 4 h, then cooled to room temperature, concentrated under diminished pressure,then treated with 2 mL of water and allowed to sit in the refrigerator overnight. The mixture was filteredand the solid washed with a small amount of cold 1:1 MeOH/water. The resulting white solid wascollected and dried under vacuum to give the unsaturated sulfone 1-2. MS (ESI”1″) = 287 (M+l).

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, Methyl 4-formylbicyclo[2.2.2]octane-1-carboxylate, other downstream synthetic routes, hurry up and to see.

Reference:
Patent; MERCK & CO., INC.; WO2006/17542; (2006); A1;,
Ester – Wikipedia,
Ester – an overview | ScienceDirect Topics