Tag: M.W=200-300

Some common heterocyclic compound, 39503-51-0, name is Methyl 5-bromo-2,4-dimethoxybenzoate, molecular formula is C10H11BrO4, 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. Product Details of 39503-51-0

To potassium isopropylidene trifluoroborate (4.87 g, 32.7 mmol) and 5-bromo-2,4-dimethoxybenzoic acid methyl ester (7.5 g, 27.3 mmol) in THF (195 ml) was added Cs2CO3 (26.6 g, 81.8 mmol) in water (39 ml). The reaction was degassed and Pd(PPh3)4 (1.58 g, 1.36 mmol) added. The reaction was heated at reflux for three days then quenched by adding water and extracted with EtOAc (x2). The combined organic layers were washed with brine, dried (MgSO4), filtered and evaporated to leave an orange solid. The product was taken up in EtOAc again and the precipitate filtered. The filtrate was evaporated to dryness to yield 5-isopropenyl-2,4-dimethoxy-benzoic acid methyl ester (6.2 g). 1H NMR (Me-Cf3-OD) 7.68 (1 H, s), 6.66 (1H, s), 5.10-5.08 (1 H, m), 5.02-5.00 (1 H, m), 3.93 (3H, s), 3.92 (3H, s), 3.84 (3H, s), 2.08-2.06 (3H, m). MS: [M+H]+ 237

These compound has a wide range of applications. It is believed that with the continuous development of the source of the synthetic route 39503-51-0, its application will become more common.

Reference:
Patent; ASTEX THERAPEUTICS LIMITED; WO2008/44041; (2008); A1;,
Ester – Wikipedia,
Ester – an overview | ScienceDirect Topics

Application of 69812-51-7, 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. 69812-51-7, name is Methyl 4-chlorosulfonylbenzoate, This compound has unique chemical properties. The synthetic route is as follows.

Preparation 102; 4-(3-Cyclopentyl-indazole-1-sulfonyl)-benzoic acid methyl ester; Combine 3-Cyclopentyl-lH-indazole (2.168 g 11.640 mmole) with triethylamine (3.526g, 34.92 mmoles) in 50 mls of dichloromethane. Dissolve 4- Chlorosulfonyl-benzoic acid methyl ester (4.085g, 17. 460mmole) in dichloromethane 50ml and add drop wise to solution at 0 C. Stir the reaction is for 12 hrs. Dilute the reaction and wash with NaHC03. Dry organic layer over MgS04 and concentrate. Purify the residue via column chromatography with a mixture of ethyl acetate and hexanes to isolate 2.046g (Yield=48. 5%) of the title compound: MS ES+385.3.

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

Reference:
Patent; ELI LILLY AND COMPANY; WO2005/66126; (2005); A1;,
Ester – Wikipedia,
Ester – an overview | ScienceDirect Topics

Application of 110661-91-1, 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. 110661-91-1, name is tert-Butyl 4-bromobutanoate belongs to esters-buliding-blocks compound, it is a common compound, a new synthetic route is introduced below.

To a solution of ethyl 1-(2-chlorophenyl)-5-(4-chlorophenyl)-4-hydroxy-1H-pyrazole-3-carboxylate (20 g, 53 mmol) in DMF (100 mL) at 0 C. was added KOtBu (7.73 g, 69 mmol). The mixture was stirred at 0 C. for 45 minutes, then tert.-butyl 4-bromobutanoate (15.4 g, 69 mmol) was added at 0 C. The reaction mixture was allowed to warm to room temperature and stir overnight. The mixture was portioned between ether and saturated aqueous NH4Cl. The organic solution was washed with water and saturated aqueous NaCl, dried over Na2SO4, and concentrated in vacuo. The residue was taken into hot cyclohexane. The mixture was allowed to stand for 72 hours. The solvent was decanted and the residue was washed with cold cyclohexane. The solid was then dried under high vacuum to yield 4-(3-tert.-butoxycarbonyl-propoxy)-1-(2-chloro-phenyl)-5-(4-chloro-phenyl)-1H-pyrazole-3-carboxylic acid ethyl ester (I-1a: 20.8 g). 1H NMR (400 MHz, CHLOROFORM-D) ppm 1.4 (s, 9H), 1.4 (t, J=7.1 Hz, 3H), 1.9 (m, 2H), 2.3 (t, J=7.5 Hz, 2H), 4.0 (t, J=5.9 Hz, 2H), 4.4 (q, J=7.1 Hz, 2H), 7.2 (m, 2H), 7.2 (m, 2H), 7.4 (m, 3H), 7.5 (m, 1H); m/z=519.0 (M+1).

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

Reference:
Patent; Pfizer Inc; US2006/241100; (2006); A1;,
Ester – Wikipedia,
Ester – an overview | ScienceDirect Topics

Application of 148547-19-7,Some common heterocyclic compound, 148547-19-7, name is Methyl 4-bromo-3-methylbenzoate, molecular formula is C9H9BrO2, 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 mixture of methyl-4-bromo-3-methylbenzoate (5.7 g, 24. 88-MMOL), lithium aluminum hydride (29 mL, 29 mmol, 1 M solution in tetrahydrofuran) and tetrahydrofuran (100 mL) is stirred in ice/water for 1 hr. The reaction is quenched with aqueous hydrochloric acid (50 mL, 1 M). The product is extracted into ethyl acetate (3 * 100 mL). The combined extracts are dried over anhydrous magnesium sulfate, filtered and concentrated. The crude product is taken up in propionitrile (100 mL). Methyl acrylate (10 mL, 121.5 mmol), palladium acetate (1.12 g, 5 mmol), tri-o-tolylphosphine (3.0 g, 10 mmol), and N, N-diisopropyl ethylamine (8.7 mL, 50 mmol) are sequentially added and the resulting reaction mixture is heated to 110 C 3 hr. The mixture is concentrated, and the residue diluted with aqueous hydrochloric acid (100 ML, 1M). The product is extracted with dichloromethane (2 * 100 mL) and ethyl acetate (100 mL). The combined extracts are dried over anhydrous magnesium sulfate, filtered, concentrated, and purified via silica chromatography eluting with 7: 3 hexanes: ethyl acetate to 1 : 1 hexanes: ethyl acetate to afford the pure product as a yellow oil, 4.7 g, 91 %. MS M+1 207. The structure is confirmed by : L H NMR spectroscopy.

The synthetic route of 148547-19-7 has been constantly updated, and we look forward to future research findings.

Reference:
Patent; ELI LILLY AND COMPANY; WO2004/63184; (2004); A1;,
Ester – Wikipedia,
Ester – an overview | ScienceDirect Topics

Synthetic Route of 17449-48-8,Some common heterocyclic compound, 17449-48-8, name is Dimethyl 5-fluoroisophthalate, molecular formula is C10H9FO4, 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.

Concentrated [HC1] (30 ml) was added to a cooled [(-5C)] suspension of dimethyl 5-amino isophthalate (20 g, 95.6 mmol) in water (75 ml), followed by portionwise addition of [NAN02] (7.5 g, 109 mmol). The reaction mixture was then stirred for 15 min. , after which [HBF4 (18] ml, 100 mmol, 48% aqueous solution) was added. The resulting mixture was stirred at [0C] for 30 min. and the precipitate formed was collected by filtration and washed with cold methanol (60 ml) and ether (60 ml). The residue was then decomposed by heating in an oil bath [(~110C).] The cooled mixture was then diluted with ether, concentrated onto silica gel and purified by flash chromatography with 5% ethyl acetate hexane as eluant giving 9.0 g (44%) of product as a white fluffy [SOLID. LH NE (CDC13), 6] [(PPM)] : 8.57 (s, 1H), 7.95 (d, 2H), 3.97 (s, 6H). A suspension of 5-fluoro-isophthalic acid dimethyl ester (1.7 g, 8. 0 mmol) in methanol (41 ml) was treated with 1.0 N sodium hydroxide (7.2 ml, 7.2 mmol). The reaction was left stirring overnight at room temperature. After the solution was concentrated, the residue was dissolved in water and transferred to a separatory funnel. The aqueous layer was washed with dichloromethane (3 times) and then acidified with 1.0 N [HC1] to pH 2. Ethyl acetate was used to extract the precipitate, which was then washed with brine and dried over anhydrous sodium sulphate. After removal of solvent in vacuo, a total of 1.3 g (83%) of 5-fluoro-isophthalic acid monomethyl ester was isolated as a white [SOLID. LH] NMR (DMSO), [5] (ppm): 8.31 (t, 1H), 7.96 (m, 2H), 3.91 (s, 3H). Triethylamine (2.2 ml, 16.0 mmol) and isobutyl [CHLOROFORMATE] (1.0 ml, 8. 0 mmol) were added to an ice-cooled solution [OF 5-FLUORO-ISOPHTHALIC] acid monomethyl ester (1.3 g, 6.7 mmol) in dichloromethane (20 ml) and then warmed to room temperature. After stirring for 2 h, the reaction mixture was filtered and concentrated. The residue was re-dissolved tetrahydrofuran (10 ml) and then sodium borohydride [(1.] 1 g, 29.02 mmol) in water (3ml) was added drop-wise. After 1 h, the reaction was quenched with methanol and then diluted with ethyl acetate, washed with water and brine, dried over anhydrous sodium sulfate, filtered and concentrated. Flash column chromatography on silica gel using 30% ethyl acetate in hexanes afforded 667 mg (54%) of 3-fluoro-5-hydroxymethyl-benzoic acid methyl ester as a colorless [OIL. 1H] NMR [(CDC13),] [8] (ppm): 7.82 (s, 1H), 7.63 (d, 1H), 7.32 (d, 1H), 4.76 (s, 2H), 3.93 (s, 3H). Ethanol (2 ml) was added to round bottom flask containing 3-fluoro-5-hydroxymethyl- benzoic acid methyl ester (667 mg, 3.6 mmol) and palladium (10 wt. % on activated carbon, 300 mg) under argon. The flask was evacuated using a water aspirator and then filled with hydrogen from a balloon. After stirring for 2 h, the palladium on carbon was removed by filtration through celite. The filtrate was then concentrated to afford 520 mg (87%) of 3-fluoro-5-methyl-benzoic acid methyl [ESTER. LH] NMR [(CDC13),] 8 (ppm): 7.65 (s, 1H), 7.51 (d, 1H), 7.08 (d, 1H), 3.91 (s, 3H), 2.40 (s, 3H). 0.5 N Lithium hydroxide (7.4 ml, 3.7 mmol) was added to a solution 3-fluoro-5-methyl- benzoic acid methyl ester (520 mg, 3.1 mmol) in tetrahydrofuran (7.4 ml). The reaction was stirred at [75 C] for 2 h and then the solvent was removed in vacuo. The residue was dissolved in a small amount of water and then acidified (pH about 2) by the addition of 10% [HC1] (aq. ). Following extraction of the aqueous layer with ethyl acetate, the organic layer was then washed with water and saturated brine, dried over anhydrous sodium sulfate, filtered, and concentrated to afford 469 mg (98%) [OF 3-FLUORO-5-METHYL-BENZOIC] acid as a white solid. 1H NMR (DMSO), d (ppm): 7.62 (s, 1H), 7.45 (d, 1H), 7.32 (d, 1H), 2.38 (s, 3H).

These compound has a wide range of applications. It is believed that with the continuous development of the source of the synthetic route Dimethyl 5-fluoroisophthalate, its application will become more common.

Reference:
Patent; ASTRA ZENECA AB; NPS PHARMACEUTICALS, INC.; WO2004/14881; (2004); A2;,
Ester – Wikipedia,
Ester – an overview | ScienceDirect Topics

Some common heterocyclic compound, 87639-57-4, name is Dimethyl 4-bromophthalate, molecular formula is C10H9BrO4, 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. COA of Formula: C10H9BrO4

Example 1; Compound No. 1: Synthesis of 4-phenyl ethynyl dimethyl phthalate; Under a nitrogen gas stream, 24.6 g of 4-bromo-dimethyl phthalate, 11.03 g of ethynyl benzene, 71 mg of triphenylphosphine, 20 mg of trans-dichloro-bis (triphenylphosphine)palladium (II) and 171 mg of cuprous iodide were placed in a three-necked flask of 300-ml capacity and, then, 60 ml of triethylamine was poured therein while stirring. The reaction mixture was refluxed for 12 hours while heating at 100 C., cooled to room temperature and, thereafter, the resultant reaction solution was filtered to remove formed salts and catalysts and, then, washed with 60 ml of toluene. The filtrate and a rinsing solution were combined and concentrated, to obtain 25.1 g of a crude crystal of 4-phenyl ethynyl diethyl phthalate. The thus-obtained crude crystal was recrystallized from a mixed system comprising 2-propanol/n-hexane (50 ml/100 ml), to thereby obtain 22.9 g of 4-phenyl ethynyl diethyl phthalate. The yield thereof was 86.4%. 1H-NMR (CDCl3): 3.92 ppm (s, 3H), 3.93 ppm (s, 3H), 7.36 to 7.39 ppm (m, 3H), 7.52 to 7.56 ppm (m, 2H), 7.66 ppm (q, 1H), 7.75 ppm (d, 1H), 7.85 ppm (d, 1H) IR vmax (KBr): 1269 (s), 1604 (m), 1724 (s), 2210 (w), 2950 (w), 3003 (w) cm-1 MS: m+/z=295 Melting point: 76.9 C. to 77.4 C.

These compound has a wide range of applications. It is believed that with the continuous development of the source of the synthetic route 87639-57-4, its application will become more common.

Reference:
Patent; FUJI PHOTO FILM CO., LTD.; US2005/215820; (2005); A1;,
Ester – Wikipedia,
Ester – an overview | ScienceDirect Topics

Related Products of 706791-83-5, 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. 706791-83-5 name is Methyl 3-amino-5-bromobenzoate, 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.

To a solution of methyl 3-amino-5-bromobenzoate (61b, 219 mg, 0.950 mmol) in 1,4-dioxane (20 mL) were added bis(pinacolato)diboron (290 mg, 1.14 mmol), PdCl2(dppf) (23 mg, 28.5 pmol) and potassium acetate (279 mg, 2.85 mmol), and then this reaction mixture was stirred at 95 C for 15 h. The reaction mixture was partitioned ethyl acetate (20 mL) and water (10 mL), and the aqueous layer was extracted with ethyl acetate (10 mL x 2). The combined organic layer was washed brine (5 mL), dried over MgS04, filtered and evaporated under reduced pressure. The residue was purified by silica gel column chromatography (hexane:ethyl acetate=4: l) to afford compound 62 (180 mg, 68%) as a white solid; NMR (400 MHz, CDC13) d 7.88 (s, 1H), 7.46 (s, 1H), 7.31 (d, J =2.4 Hz, 1H), 3.91 (s, 3H), 1.36 (s, 12H); MS (ESI, m/z) 278.2 [M+l]+; ESI-HRMS calcd. m/z for (0572) Ci4H2iN04nB 278.1564, found 278.1565 [M+l]+.

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

Reference:
Patent; THE UNITED STATES OF AMERICA, AS REPRESENTED BY THE SECRETARY, DEPARTMENT OF HEALTH AND HUMAN SERVICES; JACOBSON, Kenneth A.; YU, Jinha; CIANCETTA, Antonella; WEN, Zhiwei; JUNG, Young-Hwan; (124 pag.)WO2019/157417; (2019); 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. 106896-49-5, name is Methyl 4-amino-3-bromobenzoate, A new synthetic method of this compound is introduced below., HPLC of Formula: C8H8BrNO2

To a 250 mL round-bottom flask was added methyl 4-amino-3-bromobenzoate 32a (2.4 g, 10.43 mmol, 1.00 equiv.), 2-(3,6-dihydro-2H-pyran-4-yl)-4,4,5,5-tetramethyl-l,3,2- dioxaborolane (2.6 g, 12.38 mmol, 1.20 equiv.), dioxane (100 mL), aq. sodium bicarbonate (37 mL, 3.50 equiv, 1M), and Pd(PPh3)4 (1.21 g, 1.05 mmol, 0.10 equiv.). The resulting mixture was heated at 100C overnight. After cooling to room temperature, the mixture was diluted with 300 mL of EA and washed with brine (200 mL x 2). The organic phase was dried over anhydrous sodium sulfate and concentrated under vacuum. The crude product was purified by Flash-Prep- HPLC using the following conditions (IntelFlash-1): Column, silica gel; mobile phase, PE_EA=100:0 increasing to PE_EA=50:50 within 30 min; Detector, UV 254 nm. Removal of solvents afforded methyl 4-amino-3-(3,6-dihydro-2H-pyran-4-yl)benzoate 32b (2.4 g, 99% as a white solid.

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; ARDELYX, INC.; CHAO, Jianhua; (231 pag.)WO2019/55808; (2019); 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. 52787-14-1, name is Methyl 4-(2-methoxy-2-oxoethyl)benzoate, A new synthetic method of this compound is introduced below., category: esters-buliding-blocks

Under argon protection, 323g of PLQS-1 and 2.26L of THF were added to a 5L three-necked flask. When the temperature was lowered to -10C, 224ml of 3-bromopropyne was poured into the reaction flask, and the temperature was stirred for 0.5h to start dropping. 1.8L 1mol/L. LiHMDS solution in THF, control the dropping rate, and keep the reaction temperature at -10±3C (about 2~3h). After completion of the addition, stirring was continued for 0.5 h. HPLC detection was completed. After the reaction was completed, the reaction solution was poured into 1.25 L of acetic acid aqueous solution, stirred for 10 minutes, and then liquid-separated. The organic phase was concentrated under reduced pressure at 50 C. to remove the solvent, and the solution was concentrated. About 1.3L of isopropanol was added, and the precipitated solid was stirred and put into 0 to 5C.Cold bathThe mixture was stirred for 3 to 4 hours, filtered, and the filter cake was washed with about 300 ml of a mixed solvent of isopropanol:n-heptane = 1:6. The filter cake was dried in an oven at 50 C. to give 332 g of a pale yellow solid with a yield of 87.0%. The intermediate alpha-propargyl-(4-Methyl formate)-methyl phenylacetate (PLQS-2)The HPLC assay content is 99.6%.The HPLC content of the dipropargyl substituent was 0.3%.

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; Shandong New Age Pharmaceutical Co., Ltd.; Zhang Guimin; Chen Chengfu; Wei Chuanbing; (7 pag.)CN107488112; (2017); A;,
Ester – Wikipedia,
Ester – an overview | ScienceDirect Topics

Application of 110-38-3,Some common heterocyclic compound, 110-38-3, name is Ethyl caprate, molecular formula is C12H24O2, 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 16 (PREPARATION OF DECANOL) A dry Schlenk tube under argon was charged with 51 mg (0.15 mmol) of dysprosium (III) isopropoxide. Triethoxysilane (1.4 mL, 7.5 mmol) and ethyl decanoate (696 muL, 3 mmol) were added and the reaction mixture was heated to 60 C. After 29 hours, GLC analysis of an aliquot taken from the reaction mixture showed 23% conversion. The reaction mixture was then heated to 70 C. After an additional 3 days, THF (8 mL) and aqueous NaOH (1 N, 15 mL) were added, and the mixture was stirred vigorously for 3 hours. The reaction was worked up as in Example 13. Purification by flash chromatography (ether:hexane=3:7) afforded 224 mg (47% yield) of decanol (>95% pure by 1 H-NMR analysis) and 40 mg of recovered starting material (84% pure, 5.5% yield).

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

Reference:
Patent; Massachusetts Institute of Technology; US5220020; (1993); A;,
Ester – Wikipedia,
Ester – an overview | ScienceDirect Topics