Category: esters-buliding-blocks

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 154825-97-5 as follows. Application In Synthesis of Methyl 2-(4-bromophenyl)-2,2-dimethylacetate

Example XExample X.12-(4-Iodo-phenyl)-2-methyl-propionic acid methyl esterTo 0.45 g (1.7 mmol) 2-(4-bromo-phenyl)-2-methyl-propionic acid methyl ester (WO2008/002671) in 1.5 mL 1,4-dioxane are added 34 mg (0.18 mmol) copper(I) iodide, 0.53 g (3.5 mmol) sodium iodide and 0.04 mL (0.35 mmol) N,N’-dimethylethylendiamine under inert gas atmosphere. The mixture is stirred at 110 C. for 12 h. After cooling, the mixture is diluted with EtOAc and washed with 5% ammonia and water. The organic layer is dried over sodium sulphate. The solvent is evaporated to yield the desired product.C11H13IO2 (M=304.12 g/mol)ESI-MS: 305 [M+H]+Rt (HPLC): 2.21 min (method C)

According to the analysis of related databases, 154825-97-5, the application of this compound in the production field has become more and more popular.

Reference:
Patent; BOEHRINGER INGELHEIM INTERNATIONAL GMBH; US2012/214782; (2012); A1;,
Ester – Wikipedia,
Ester – an overview | ScienceDirect Topics

Adding a certain compound to certain chemical reactions, such as: 820236-81-5, name is Methyl 2-bromo-6-fluorobenzoate, 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 820236-81-5, Safety of Methyl 2-bromo-6-fluorobenzoate

Step B: methyl 2-fluoro-6-vinylbenzoate To a solution of methyl 2-bromo-6-fluorobenzoate (53 g, 0.228 mol) and potassium trifluoro(vinyl)borate (33.63 g, 0.251 mol) in dioxane and H2O (3:1, 600 mL) was added Pd(dppf)Cl2 (5 g, 6.84 mmol) and sodium carbonate (69 g, 0.684 mol) at RT. The reaction mixture was heated at 100 C. for 12 hours under a nitrogen atmosphere. The mixture was concentrated in vacuo, diluted with water, and extracted with EtOAc (3*200 mL). The combined organic layers were washed with brine, dried over anhydrous Na2CO3, filtered, and concentrated. The crude product was purified by column chromatography eluting with a gradient of EtOAc (1-100%) and PE to give the title compound (31.4 g, 76.5%). 1H NMR (400 MHz, CDCl3) delta ppm 7.45-7.36 (m, 2H), 7.03-7.02 (m, 1H), 6.88-6.81 (m, 1H), 5.77-5.73 (m, 1H), 5.41-5.39 (d, J=10.8 Hz, 1H), 3.95 (s, 3H).

At the same time, in my other blogs, there are other synthetic methods of this type of compound, Methyl 2-bromo-6-fluorobenzoate, and friends who are interested can also refer to it.

Reference:
Patent; Takeda Pharmaceutical Company Limited; Lawson, John David; Sabat, Mark; Scorah, Nicholas; Smith, Christopher; Vu, Phong H.; Wang, Haixia; US2014/256734; (2014); A1;,
Ester – Wikipedia,
Ester – an overview | ScienceDirect Topics

Reference of 85953-29-3, 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. 85953-29-3, name is Methyl 2-chloro-4-fluorobenzoate, This compound has unique chemical properties. The synthetic route is as follows.

Step A. 2-Chloro-4-(3-methyl-1H-pyrazol-1-yl)-benzoic acid methyl ester Under anhydrous conditions a stirred suspension of hexane washed potassium hydride (0.424 g, 10.6 mmol) in 5 mL of dimethylformamide was treated in one portion with 3-methyl pyrazole (0.85 mL, 10.6 mmol). After the gas evolution ceased, 2-chloro-4-fluorobenzoic acid methyl ester (2.0 g, 10.6 mmol) was added to the clear solution. The mixture was heated at 130 C. for 15 minutes, cooled, and partitioned between ethyl acetate and brine. The organic layer was washed with water and brine, and dried over sodium sulfate. Removal of solvent afforded 2.2 g of a yellow oil consisting of a mixture of 3-methyl and 5-methylpyrazole regioisomers. In addition, about 20% of the acid derived from hydrolysis of the ester was detected by analysis of the NMR spectrum of the crude product. The desired 3-methylpyrazole regioisomer was separated from the 5-methyl isomer of Example 22 by flash chromatography (on silica Merck-60, dichloromethane-hexane 2:1) and was isolated as a white solid (1.55 g, 56%). NMR (DMSO-d6, 400 MHz): delta 2.264 (s, 3H, CCH3), 3.845 (s, 3H, OCH3), 6.40 (d, 1H), 7.865 (dd, 1H), 7.93 (d, 1H), 8.00 (s, 1H), 8.535 (d, 1H). MS (EI, m/z): 250/252 [M]+, 219.

The chemical industry reduces the impact on the environment during synthesis Methyl 2-chloro-4-fluorobenzoate. I believe this compound will play a more active role in future production and life.

Reference:
Patent; American Home Products Corporation; US6194407; (2001); B1;,
Ester – Wikipedia,
Ester – an overview | ScienceDirect Topics

Synthetic Route of 764667-64-3, 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. 764667-64-3, name is 5-(1-Hydroxy-2-(2,4,5-trifluorophenyl)ethylidene)-2,2-dimethyl-1,3-dioxane-4,6-dione, This compound has unique chemical properties. The synthetic route is as follows.

A round bottom flask is charged with 3-trifluoromethyl-5,6,7,8-tetrahydro- 1 ,2,4-thazolo[4,3a]pyrazine hydrochloride (144.6 g) and ethyl acetate (2000 ml_) at 28C, then N-methylmorpholine (67.2 g) is added. 5-[1 -hydroxy-2-(2,4,5- trifluorophenyl)ethyledine]-2,2-dimethyl-1 ,3 dioxane-4,6-dione (200 g) is added and the mixture is heated to reflux for 6 hours. The mixture is slowly cooled to room temperature. Water (1000 ml_) is added, the mixture is stirred for 15 minutes, and the organic layer is separated. The aqueous layer is extracted with ethyl acetate (200 ml_). The two organic layers are combined and solvent is distilled at 37C. Toluene (400 ml_) is added to the residue and stirred for 3 hours. The solid is filtered, washed with toluene (200 ml_), and dried under reduced pressure at 500C for 12.5 hours, to afford the title compound. (252.0 g, 98.1 % yield).

The chemical industry reduces the impact on the environment during synthesis 5-(1-Hydroxy-2-(2,4,5-trifluorophenyl)ethylidene)-2,2-dimethyl-1,3-dioxane-4,6-dione. I believe this compound will play a more active role in future production and life.

Reference:
Patent; DR. REDDY’S LABORATORIES LTD.; DR. REDDY’S LABORATORIES, INC.; BANDICHHOR, Rakeshwar; GUDIMALLA, Nagaraju; DWIVEDI, Namrata; CHETLURU, Kiran Kumar; GADE, Srinivas Reddy; MUVVA, Venkateswarlu; SRIVASTAVA, Bindu; WO2011/25932; (2011); A2;,
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. 18595-14-7, name is Methyl 4-amino-3-methylbenzoate, This compound has unique chemical properties. The synthetic route is as follows., name: Methyl 4-amino-3-methylbenzoate

To a stirred solution of 4-amino-3-methyl-benzoic acid methyl ester (11.55 g, 70 mmol) and 3-bromobenzaldehyde (8.2 mL, 70 mmol) in acetonitrile (150 mL) were added isobutene (17 mL, 242 mmol) and ytterbium(III) trifluoromethanesulfonate (Yb(OTf)3) (5.2 g, 8.4 mmol). The resulting mixture was stirred at 90 C. for 20 h in sealed tube. The mixture was diluted with ethyl acetate (300 mL) and washed with water (100 mL×2) and brine (100 mL×2) and then dried over anhydrous sodium sulfate. The solvent was removed in vacuo and the residue was purified by ISCO combi-flash chromatography (gradient elution, 10-50% ethyl acetate in petroleum ether) to afford 2-(3-bromo-phenyl)-4,4,8-trimethyl-1,2,3,4-tetrahydro-quinoline-6-carboxylic acid methyl ester (8.15 g, 30%) as a light yellow solid: MS (ESI) M+1=388.0 & 390.0.

According to the analysis of related databases, 18595-14-7, the application of this compound in the production field has become more and more popular.

Reference:
Patent; Feng, Lichun; Huang, Mengwei; Liu, Yongfu; Wu, Guolong; Yan, Shixiang; Yun, Hongying; Zhou, Mingwei; US2012/190677; (2012); A1;,
Ester – Wikipedia,
Ester – an overview | ScienceDirect Topics

Adding a certain compound to certain chemical reactions, such as: 6942-37-6, name is Methyl 5-amino-2-bromobenzoate, 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 6942-37-6, Safety of Methyl 5-amino-2-bromobenzoate

To a cooled (5 C.) solution of 48 (4.46 g, 19.4 mmol), pyridine (8 mL, 7.6 g, 97 mmol) in DCM (90 mL) was added dropwise over a period of 20 min a solution of methanesulfonyl chloride (1.65 ml, 2.43 g, 21.3 mmol) in DCM (10 mL). The reaction mixture was stirred at RT overnight and then poured into aq. 1N HCl solution. The resulting solution was extracted with EtOAc, washed with brine, dried (MgSO4), filtered and concentrated to afford 5.7 g (95%) of 50.

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 5-amino-2-bromobenzoate, other downstream synthetic routes, hurry up and to see.

Reference:
Patent; Chin, Elbert; Li, Jim; Lui, Albert Sui-Ting; Talamas, Francisco Xavier; US2010/297073; (2010); A1;,
Ester – Wikipedia,
Ester – an overview | ScienceDirect Topics

Adding a certain compound to certain chemical reactions, such as: 344-14-9, name is Dimethyl 2-fluoromalonate, 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 344-14-9, Safety of Dimethyl 2-fluoromalonate

Example 1; Mixture of dimethyl fluoro[(1R,5R)-5-hydroxycyclopent-2-en-1-yl]propanedioate (10a) and dimethyl fluoro[(1S,5S)-5-hydroxycyclopent-2-en-1-yl]propanedioate (10b) 23.01 g (110.2 mmol) of a 25 w/w % methanol solution of sodium methoxide was added to a methanol (90.4 mL) solution of 18.19 g (121.2 mmol) of dimethyl fluoropropanedioate (9) over 3 minutes while keeping the internal temperature between 25 C. and 30 C. After stirring the solution thus obtained for 15 minutes, 4.52 g (55.1 mmol) of 6-oxabicyclo[3.1.0]hex-2-ene (8) was added thereto over 2 minutes while keeping the internal temperature between 25 C. and 38 C. After stirring at room temperature for 1 hour, 45 mL of a saturated ammonium chloride aqueous solution was added over 10 minutes while keeping the internal temperature between 26 C. and 35 C. The reaction mixture was concentrated under reduced pressure, most of the methanol was removed by evaporation, and 108 g of a brown solution containing solids was obtained. After extraction with 136 mL of ethyl acetate was carried out twice, washing with 45 mL of water was carried out. After the organic layer was concentrated under reduced pressure, 100 mL of toluene was added, and concentration under reduced pressure was carried out again. The concentrated residue was purified by flash silica gel column chromatography (eluent: toluene/ethyl acetate), thus giving 7.21 g of a mixture of the compound of Formula 10a and the compound of Formula lab as a yellow oily material.1H NMR (500 MHz, DMSO-d6): delta 2.13-2.17 (m, 1H), 2.56 (dddd, J=2.2, 4.3, 7.1, 17.2 Hz, 1H), 3.32-3.40 (m, 1H), 3.77 (s, 3H), 3.79 (s, 3H), 4.20 (m, 1H), 5.04 (d, J=6.1 Hz, 1H), 5.47 (ddd, J=2.1, 4.3, 6.1 Hz, 1H), 5.85 (ddd, J=2.2, 4.4, 6.1 Hz, 1H).13C NMR (125 MHz, DMSO-d6) delta 41.93, 53.39 (d, J=19.5 Hz), 58.70 (d, J=20.8 Hz), 70.43 (d, J=2.6 Hz), 93.55, 95.14, 125-59, 133.32, 165.42 (d, J=15.6 Hz), 165.62 (d, J=14.3 Hz). 19F NMR (470 MHz, DMSO-d6); delta -172.43, -172.36. HRMS (ES) m/z:[M+Na]+ calcd for C10H13O5FNa; 255.0645, found 255.0635. IR (neat) 3528, 3408, 2960, 1755, 1438, 1284, 1253, 1173, 1111, 1060, 1031, 936, 838, 787, 722, 668, 415 cm-1,

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 2-fluoromalonate, other downstream synthetic routes, hurry up and to see.

Reference:
Patent; TAISHO PHARMACEUTICAL CO., LTD.; US2011/65934; (2011); A1;,
Ester – Wikipedia,
Ester – an overview | ScienceDirect Topics

Synthetic Route of 4224-69-5, The chemical industry reduces the impact on the environment during synthesis 4224-69-5, name is Methyl 2-(bromomethyl)acrylate, I believe this compound will play a more active role in future production and life.

(7E)-(1R,3R,20R)-1,3-di-(tert-butyldimethylsilyloxy)-2-methylene-9,10-seco-19-nor-20-[(2S)-hydroxy-4-methoxycarbonyl-4-penten-1-yl]-5,7-pregnandiene (10) and (7E)-(1R,3R,20R)-1,3-di-(tert-butyidimethylsilyloxy)-2-methylene-9,10-seco-19-nor-20-[(2R)-hydroxy 4-methoxycarbonyl-4-penten-1-yl]-5,7-pregnandiene (1); To a solution of 9 (25 mg, 425 mumol) in saturated aqueous NH4Cl solution/THF (5:1, 3 mL) were added methylbromomethylacrylate (10 muL, 85 mumol) (commercially available from Sigma-Aldrich) and activated Zn dust (11 mg, 0.17 mmol) at 0 C., and the mixture was stirred at the same temperature for 1.5 hours. The mixture was diluted with EtOAc. The organic layer was washed with saturated aqueous NaCl solution, dried over MgSO4, and concentrated. The residue was purified by flash column chromatography on silica gel (5% EtOAc/hexanes) to give 10 (5 mg, 7.3 mumol, 57%) and 11 (4 mg, 5.5 mumol, 43%) as colorless oils, respectively. 10: 1H NMR (CDCl3, 400 MHz) delta 6.25(s, 1H, =CH2), 6.21 (d, J=11.2 Hz, 1H, 6-H), 5.84 (d, J=11.2 Hz, 1H, 7-H), 5.67 (s, 1H, =CH2), 4.97 (s, 1H, =CH2), 4.91 (s, 1H, =CH2), 4.42 (m, 2H, 1beta- and 3alpha-H), 3.87 (m, 1H, CH-OH), 3.77 (s, 3H, -CO2CH3), 2.82 (br d, J=11.3, 1H), 2.56-2.44 (m, 3H), 2.40-2.25 (m, 2H), 2.18 (m, 1H), 0.97 (d, J=6.6 Hz, 3H), 0.90 (s, 9H, Si-t-Bu), 0.85 (s, 9H, Si-t-Bu), 0.57 (s, 3H), 0.08, 0.06, 0.05, and 0.02 (each s, each 3H, 4× SiCH3); 13C NMR (CDCl3) delta 168.31, 153.19, 141.28, 137.76, 133.03, 127.92, 122.58, 116.41, 106.44, 72.79, 71.78, 67.85, 57.35, 56.54, 52.28, 47.85, 46.00, 43.93, 41.78, 40.86, 38.72, 33.09, 28.94, 28.08, 26.04, 25.97, 23.62, 22.44, 18.87, 18.45, 18.35, 12.35, -4.67 (SiMe), 4.90 (3× SiMe); exact mass calculated for C40H70O5Si2Na [M+Na]+ 709.4660, found 709.4680. 11: 1H NMR (CDCl3, 400 MHz) delta 6.29 (s, 1H, =CH2), 6.22 (d, J=11.1 Hz, 1H, 6-H), 5.84 (d, J=11.1 Hz, 1H, 7-H), 5.70 (s, 1H, =CH2), 4.98 (s, 1H, =CH2), 4.93 (s, 1H, =CH2), 4.43 (m, 2H, 1beta- and 3alpha-H), 3.90 (m, 1H, CH-OH), 3.79 (s, 3H, -CO2CH3), 2.84 (br d, J=12.1 Hz, 1H), 2.71 (dd, J=13.8, 1.7 Hz, 1H), 2.56-2.42 (m, 2H), 2.34 (m, 1H), 1.03 (d, J=6.4 Hz, 3H), 0.90 (s, 9H, Si-t-Bu), 0.87 (s, 9H, Si-t-Bu), 0.57 (s, 3H), 0.09, 0.08, 0.06, and 0.04 (each s, each 3H, 4× SiCH3); 13C NMR (CDCl3), delta 168.30, 153.17, 141.23, 137.77, 133.04, 128.07, 122.58, 116.41, 106.46, 72.72, 71.83, 69.45, 57.47, 56.43, 52.28, 47.80, 45.91, 44.13, 40.81, 40.27, 38.77, 34.39, 28.93, 28.12, 26.03, 25.98, 23.61, 22.42, 19.55, 18.74, 18.37, 12.29, -4.67 (3× SiMe), -4.88 (SiMe); exact mass calculated for C40H70O5Si2 [M]+ 686.4762, found 686.4789.

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 2-(bromomethyl)acrylate, other downstream synthetic routes, hurry up and to see.

Reference:
Patent; Wisconsin Alumni Research Foundation; US2006/223782; (2006); A1;,
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

Reference of 4630-80-2,Some common heterocyclic compound, 4630-80-2, name is Methyl cyclopentanecarboxylate, molecular formula is C7H12O2, 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 168 Preparation of 1-(4-Bromobutyl)cyclopentane Carboxylic Acid Methyl Ester To a solution of diisopropylamine (150 mmol, 21 mL) in THF (100 mL) was added dropwise a solution of n-butyl lithium (145 mmol, 58 mL, 2.5M) in hexanes at -10 C. while maintaining the temperature below 0 C. After addition, the solution was stirred for 30 min at 0 C. To this a solution of methyl cyclopentane carboxylate (100 mmol, 13.1 g) in THF (20 mL) was added dropwise at -70 C. maintaining the internal temperature between -60 to -70 C. After addition, the reaction mixture was stirred for 1 h at -50 to -60 C. Then, a solution of 1,4-dibromobutane (100 mmol, 21.59 g) in THF (20 mL) was added dropwise and the light brown suspension was stirred for 1 h at -60 to -70 C. Then, it was allowed to warm to room temperature and stirred overnight. The reaction mixture was poured into a saturated solution of ammonium chloride (200 mL) and the organic compound was extracted into ether (2*100 mL). The combined extracts were washed with a saturated brine solution (150 mL) and dried over anhydrous magnesium sulfate. After filtration of the drying agent, the solution was concentrated under vacuum and the resulting residue was distilled at 120-133 C./2.5 mm Hg to obtain 1-(4-bromobutyl)cyclopentane carboxylic acid methyl ester as a colorless oil (12.8 g, 48%). HR MS (C11H19BrO2): Obs mass, a 262.0565. Calcd mass, 262.0568 (M+).

These compound has a wide range of applications. It is believed that with the continuous development of the source of the synthetic route Methyl cyclopentanecarboxylate, its application will become more common.

Reference:
Patent; Hoffmann-La Roche Inc.; US6455550; (2002); B1;,
Ester – Wikipedia,
Ester – an overview | ScienceDirect Topics