Month: May 2021

Application of 1070-64-0,Some common heterocyclic compound, 1070-64-0, name is Ethyl 6,8-dichlorooctanoate, molecular formula is C10H18Cl2O2, 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.

600 kg (2.48 kmol) racemic 6,8-dichloroethyl caprylate and 78 kg (2.43 kmol, 0.98 equiv.) sulphur in 576 kg ethanol were placed in a 6 m3 reactor with stirrer, metering pump, pressure and internal temperature measurement and also jacket heating. At an internal temperature of 110 C. and a pressure of 0.35 MPa, 2062 kg of an aqueous sodium sulphide solution (12.3 wt. %) comprising 253.6 kg Na2S (3.24 kmol, 1.31 equiv.) was metered in uniformly with stirring over a period of 85 min. The reaction mixture was stirred for another 120 min at 110 C. Then 508 g of a solution of sodium borohydride (12 wt. %) in sodium hydroxide solution (40 wt. %) comprising 61.0 kg NaBH4 (1.61 kmol, 0.65 equiv.) was metered in uniformly within 90 min. at 70 C. The ethanol contained was distilled off from the reaction mixture to the greatest possible extent, and thereupon a further 253 kg of a solution of sodium borohydride (12 wt. %) in sodium hydroxide solution (40 wt. %) comprising 30.4 kg NaBH4 (0.80 kmol, 0.32 equiv.) added over a period of 60 min. at 70 C. Once addition had taken place, the mixture was heated to boiling and stirred further for 30 min. at this temperature. After cooling, 540 kg MTBE was added and the batch was acidified to a pH value of 2.6 to 3.0 by adding 1454 kg (12.3 kmol) hydrochloric acid (31 wt. %). The organic phase was separated off and the organic solvent was distilled off completely without a vacuum. 506 kg of a yellow liquid was obtained, with a content of 94.0 wt. % dihydrolipoic acid and a polymer content of 5.6 wt. % (corresponds to a yield of 91.8% of theory).

These compound has a wide range of applications. It is believed that with the continuous development of the source of the synthetic route Ethyl 6,8-dichlorooctanoate, its application will become more common.

Reference:
Patent; ALZCHEM TROSTBERG GMBH; SCHNAPPERELLE, Ingo; WINKLER, Stephan; SANS, Juergen; THALHAMMER, Franz; (7 pag.)US2019/276396; (2019); A1;,
Ester – Wikipedia,
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Electric Literature of 25081-39-4, 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. 25081-39-4 name is Methyl 3,5-dimethylbenzoate, 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.

3-Bromomethyl-5-methyl-benzoic acid methyl ester (LW003036B) and 3,5-Bis- bromomethyl-benzoic acid methyl ester (LWO03036C); To a solution of methyl 3,5-dimethylbenzoate (15.0 g, 89.52 mmol) in carbon tetrachloride (molecular sieves 4 A dried, 150 mL) was added finely powdered N- bromosuccinimide (16.1 g, 89.52 mmol) and benzoyl peroxide (> 97%, 200 mg). The light yellow suspension was then refluxed which turned into a light orange suspension after about 10 min. When the colour of the suspension returned to light yellow again about 45 min later, the reflux was terminated. After cooling to room temperature, the suspension was filtered and the filter cake collected was washed with ether (5 x 30 mL). The combined filtrates were evaporated to give a clear bright yellow liquid (22.9 g) which was fractionated by flash chromatography (silica: 700 g; eluent: ethyl acetate/hexane, 1 : 10 to 1 : 1). The second fraction that collected upon evaporation gave LW003036B as a translucent pale yellow oil (13.32 g, 54.79 mmol, 61%) whereas the third fraction gave LW003036C as white fluffy needle-shaped crystals (1.99 g, 3.08 mmol, 7%). LW003036B: Rf: 0.27 (ethyl acetate/hexane, 1: 8), c. f. 0.39 (S.M.) No.H (270 MHz, CDC13) 2.39 (3H, s, Ar-CH3), 3.90 (3H, s, COOMe), 4.47 (2H, s, CH2Br), 7.39 (1H, slightly broad s, Ar), 7.78 (1H, slightly broad s, Ar) and 7.85 (1H, s, Ar). LRMS (FAB+): 443.3 (17), 398.3 [25, (M81Br+H+NBA) +], 243.1 [100, (M79Br+H)+], 163.1 [83, (M79Br-79Br) +], 85.1 (54). HRMS (FAB+) : 243.00124 C10H12O2Br requires 243.00207 LW003036C: Rf: 0.20 (ethyl acetate/hexane, 1:8), c.f. 0.39 (S.M.) m. p. 100-103 C [Lit.l (from column), 95-97 C] (at) Liu P, Chen Y, Deng J, Tu Y. An efficient method for the preparation of benzylic bromides. Synthesis 2001,14: 2078- 2080. No.H (400 MHz, CDC13) 3.93 (3H, s, OCH3), 4.49 (4H, s, 2 x CH2), 7.60 (1H, t, J- 1.7 Hz, C4-H) and 7.97 (2H, d, J- 2.0 Hz, C2-H and C6-H).; 3-Bromomethyl-5-methyl-benzoic acid methyl ester (LW003015B) and 3,5-Bis- bromomethyl-benzoic acid methyl ester (LWO03015C); To a solution of methyl 3,5-dimethylbenzoate (5.57 g, 33.24 mmol) in carbon tetrachloride (molecular sieves 4 A dried, 50 mL) was added finely powdered N- bromosuccinimide (5.98 g, 33.24 mmol) and benzoyl peroxide (No. 97%, 100 mg). The light yellow suspension was then refluxed which turned into a light orange suspension after about one hour. When the colour of the suspension returned to light yellow again about 30 min later, the reflux was terminated. After cooling to room temperature, the suspension was filtered and the filter cake collected was washed with ether (5 x 30 mL). The combined filtrates were evaporated to give a clear bright yellow liquid (8.15 g) which was fractionated by flash chromatography (silica: 300 g; eluent: ethyl acetate/hexane, 1 : 10; flow rate: ca. 30 mL/min). The first fraction collected was the starting material (998 mg). The second and third fractions collected were respectively LW003015B as a translucent pale yellow oil (4.90 g, 20.16 mmol, 61%) and LW003015C as white fluffy needle-shaped crystals (990 mg, 3.08 mmol, 9%). LW003015B Rf: 0.27 (ethyl acetate/hexane, 1: 8), c. f. 0.39 (S.M.) No.H (270 MHz, CDC13) 2.39 (3H, s, Ar-CH3), 3.90 (3H, s, COOMe), 4.47 (2H, s, CH2Br), 7.39 (1H, slightly broad s, Ar), 7.78 (1H, slightly broad s, Ar) and 7.85 (1H, s, Ar). LRMS (FAB+) : 443.3 (17), 398.3 [25, (M81Br+H+NBA) +], 243.1 [100, (M79Br+H)+], 163.1 [83, (M79Br-79Br) +], 85.1 (54). HRMS (FAB+): 243.00124 ClOH1202Br requires 243.00207. LW003015C Rf: 0.20 (ethyl acetate/hexane, 1: 8), c. f. 0.39 (S.M.) m. p. 100-103 C [Lit. (at) (from column), 95-97 C] (at) ¹ Liu P, Chen Y, Deng J, Tu Y. An efficient method for the preparation of benzylic bromides. Synthesis 2001,14: 2078- 2080. No.H (400 MHz, CDC13) 3.93 (3H, s, OCH3), 4.49 (4H, s, 2 x CH2), 7.60 (1H, t, J- 1.7 Hz, C4-H) and 7.97 (2H, d, J- 2.0 Hz, C2-H and C6-H).

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

Reference:
Patent; STERIX LIMITED; WO2005/118560; (2005); 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. 19376-57-9, name is Methyl 4,4,4-trichlorobutanoate, This compound has unique chemical properties. The synthetic route is as follows., Recommanded Product: 19376-57-9

To a stirred solution of methyl 4,4,4-trichlorobutanoate 2 (1.35 g, 6.57 mmol) in DCM (30 mL) at -78 C was added DIBAL-H (6.57 mL, 6.57 mmol, 1.0 M in hexanes) at a rate of 1.0 mL/min. The reaction mixture was stirred at -78 C for 1 h. After successive addition of MeOH (7 mL), HC1 (25 mL, 1 M) and Rochelle salt solution (25 mL, 1 M), the reaction mixture was stirred at room temperature for another 1 h. The separated organic layer was washed with brine, dried over anhydrous MgSO4, filtered, and concentrated in vacuo. The crude residue was purified by silica gel flash chromatography eluting with hexanes/EtOAc (20:1) to afford 4,4,4-trichlorobutanal 3 (1.15 g, 5.78 mmol) as a colourless oil in a yield of 88 %. ?H NMR (400 MHz, CDC13) S9.85 (br. s., 1H), 3.03-3.11 (m, 2H), 2.96-3.02 (m, 2H); ?3CNMR(100 MHz, CDC13) S 198.5, 98.9, 47.5, 41.2.

According to the analysis of related databases, 19376-57-9, the application of this compound in the production field has become more and more popular.

Reference:
Patent; BRITISH COLUMBIA CANCER AGENCY BRANCH; THE UNIVERSITY OF BRITISH COLUMBIA; YAN, Luping; ANDERSEN, Raymond, J.; SADAR, Marianne, Dorothy; MAWJI, Nasrin, R.; BANUELOS, Carmen, Adriana; WO2015/184393; (2015); A1;,
Ester – Wikipedia,
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Electric Literature of 24393-53-1, 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. 24393-53-1 name is (E)-Ethyl 3-(4-bromophenyl)acrylate, 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.

A method for constructing a quaternary carbon ring by visible light catalysis [2+2] reaction, comprising the following steps: The ruthenium complex 1 is used as a visible light catalyst, and 1.3 mg of the catalyst is added to 2 mL of 1,2-dichloroethane.0.2 mmol of (E)-ethyl-3-p-bromophenyl acrylate (corresponding R2 is p-bromophenyl, R3 is ethoxy), 1.0 mmol of 1,1-diphenylethylene (corresponding R1 is benzene) The base, R2 is a phenyl group) wherein the concentration of the visible light catalyst is 1.0 x 10-3 M. Pass argon for ten minutes,Then, with 450 nm ± 10 nm Blue LEDs, the light was illuminated in an argon atmosphere at 25 C for 5 h.After the reaction is completed, it is directly dried and separated by a column. Nuclear magnetic resonance spectrum, carbon spectrum,Mass spectrometryThe compound is a racemic ethyl-(2R)-2-(p-bromophenyl)-3,3-diphenyl-cyclobutyl-1-carboxylate.The conversion of the starting material was 100% and the yield of the cyclobutane product was 85%.

At the same time, in my other blogs, there are other synthetic methods of this type of compound, (E)-Ethyl 3-(4-bromophenyl)acrylate, and friends who are interested can also refer to it.

Reference:
Patent; Chinese Academy Of Sciences Physics And Chemistry Technology Institute; Wu Lizhu; Lei Tao; Zhao Leimin; Zhou Chao; Liu Zan; Tong Zhenhe; (89 pag.)CN108623425; (2018); A;,
Ester – Wikipedia,
Ester – an overview | ScienceDirect Topics

Reference of 87661-20-9,Some common heterocyclic compound, 87661-20-9, name is tert-Butyl cyclopropanecarboxylate, molecular formula is C8H14O2, 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 4ATert-Butyl(+/-)-1-(4-bromopentyl)cyclopropanecarboxylate 21.2 ml (52.7 mmol) of a 2.5 M solution of n-butyllithium in n-hexane were added dropwise to a solution, cooled to -78 C., of 7.4 ml (52.7 mmol) of diisopropylamine in 20 ml of abs. THF. During the addition, the reaction temperature was kept below -60 C. After 30 min of stirring at -60 C. to -70 C., this solution was added dropwise to a solution, cooled to -78 C., of 5.0 g (35.2 mmol) of tert-butyl cyclopropanecarboxylate and 16.2 g (70.3 mmol) of 1,4-dibromopentane in 20 ml of abs. THF. After the end of the addition, cooling was removed and the mixture was slowly warmed to RT with stirring. After a further 4 h of stirring at RT, the reaction mixture was added to saturated aqueous ammonium chloride solution. The mixture was extracted three times with dichloromethane. The combined organic phases were dried over magnesium sulfate and concentrated under reduced pressure. The product was purified by chromatography on silica gel (mobile phase gradient cyclohexane/dichloromethane 50:1 to 5:1). This gave, in two batches, in total 5.73 g (53.6% of theory) of the target compound.MS (DCI): m/z=308/310 (M+NH4)+.GC-MS (Method 1): Rt=4.82 min; m/z=234 (M-C4H8)+.1H-NMR (400 MHz, DMSO-d6): delta=4.29 (q, 1H), 1.78-1.71 (m, 2H), 1.67 (d, 3H), 1.65-1.43 (m, 4H), 1.39 (s, 9H), 0.98 (m, 2H), 0.67 (m, 2H).

The synthetic route of 87661-20-9 has been constantly updated, and we look forward to future research findings.

Reference:
Patent; BAYER PHARMA AKTIENGESELLSCHAFT; US2012/28971; (2012); A1;,
Ester – Wikipedia,
Ester – an overview | ScienceDirect Topics

Application of 14920-81-1, 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. 14920-81-1, name is Methyl 2,6-dimethylbenzoate belongs to esters-buliding-blocks compound, it is a common compound, a new synthetic route is introduced below.

To a solution of methyl 2,6-dimethylbenzoate (described in J. Am. Chem. Soc., 99, 6405 (1977); 23.4 g, 143 mmol) in dichloroethane (200 ml) were added N-bromosuccinimide (25.46 g, 143 mmol) and alpha,alpha’-azobisisobutyronitrile (234.8 mg, 1.43 mmol), and the mixture was irradiated with visible light (tungsten lamp, 375 W) for 1 hour. After cooling the reaction mixture, the precipitated material was filtered off, and the solvent was distilled off under reduced pressure. The obtained oily residue was subjected to chromatography on a silica gel (200 g) column (eluent; ethyl acetate : hexane = 1 : 10) to give an oily mixture containing ca. 50% methyl 2-(bromomethyl)-6-methylbenzoate. The mixture was dissolved in dimethyl sulfoxide (150 ml), and sodium acetate (16.4 g, 0.2 mol) was added thereto. The resulting mixture was stirred at room temperature for 2 hours, then a saturated aqueous solution of ammonium chloride was added thereto, and the product was extracted with ethyl acetate. The organic layer was washed with a saturated aqueous solution of sodium chloride, and the solvent was distilled off under reduced pressure to give an oily residue. The residue was subjected to chromatography on a silica gel (200 g) column (eluent; ethyl acetate : hexane = 1 : 10 ~ 1 : 3) to give methyl 2-(acetoxymethyl)-6-methylbenzoate (8.09 g, more than 80% content) as a colorless oil. The obtained methyl 2-(acetoxymethyl)-6-methylbenzoate was used for the following reaction without further purification. NMR spectrum (400 MHz, CDCl3) delta ppm: 2.07 (3H, s), 2.38 (3H, s), 3.92 (3H, s), 5.15 (2H, s), 6.99-7.12 (3H, m). Methyl 2-(acetoxymethyl)-6-methylbenzoate obtained above was dissolved in methanol (80 ml), and potassium carbonate (251.5 mg, 1.8 mmol) was added thereto. The mixture was stirred at room temperature for 2 hours, then a 2N aqueous solution of hydrochloric acid (3 ml) was added thereto, and the solvent was distilled off under reduced pressure. The obtained solid residue was dissolved in ethyl acetate, and the solution was washed with a saturated aqueous solution of sodium chloride and then the solvent was distilled off under reduced pressure. The solid residue was subjected to chromatography on a silica gel (100 g) column (eluent; ethyl acetate : hexane = 1 : 2) to afford 7-methyl-1(3H)-isobenzofuranone (5.18 g, more than 80% content). The obtained 7-methyl-1(3H)-isobenzofuranone was used for the following reaction without further purification. NMR spectrum (400 MHz, CDCl3) delta ppm: 2.71 (3H, s), 5.23 (2H, s), 7.25-7.30 (2H, m), 7.56 (1H, t, J=8 Hz). A solution of the 7-methyl-1(3H)-isobenzofuranone obtained above in tetrahydrofuran (80 ml) was cooled to 0C, and lithium borohydride (1.90 g, 87.2 mmol) was added thereto. The mixture was stirred at 60C for 2 hours, then cooled to 0C, and a 2N aqueous solution of hydrochloric acid (50 ml) was added dropwise. The product was extracted with ethyl acetate, and the solvent was evaporated under reduced pressure to give an oily residue. The residue was subjected to chromatography on a silica gel (75 g) column (eluent; ethyl acetate : hexane = 2 : 1 ? 1 : 0) to afford the title compound (4.17 g, 19% total yield from methyl 2,6-dimethylbenzoate) as an oil. NMR spectrum (400 MHz, CDCl3) delta ppm: 2.45 (3H, s), 4.76 (2H, s), 4.79 (2H, s), 7.17-7.22 (3H, m) IR spectrum nu max CHCl3 cm-1: 3605, 1469, 1380, 1002 Mass spectrum m/z (EI): 152 (M+).

The synthetic route of Methyl 2,6-dimethylbenzoate has been constantly updated, and we look forward to future research findings.

Reference:
Patent; Sankyo Company, Limited; EP1362856; (2003); 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 61500-87-6 as follows. Safety of Methyl 2-amino-4-(trifluoromethyl)benzoate

General procedure: To a solution of methyl 2-amino-4-fluorobenzoate (1.64 g, 9.71 mmol) and methanesulfonyl chloride (5.28 mL, 115 mmol) in dichloromethane (100 mL) was added pyridine (7.86 mL, 97.1 mmol). The solution was stirred at room temperature for 18 hours. The reaction was quenched with 1N HCl and was stirred for 5 minutes. The mixture was extracted with DCM (3×). The combined organic layers were washed with brine, dried over anhydrous MgSO4, filtered and concentrated. The crude product was purified by silica gel chromatography to afford methyl 4-fluoro-2-(methylsulfonamido)benzoate.

According to the analysis of related databases, 61500-87-6, the application of this compound in the production field has become more and more popular.

Reference:
Patent; Gilead Sciences, Inc.; Farand, Julie; Kaplan, Joshua A.; Notte, Gregory; Olen, Casey Lockwood; Sangi, Michael; Sperandio, David; (115 pag.)US2019/359565; (2019); A1;,
Ester – Wikipedia,
Ester – an overview | ScienceDirect Topics

Synthetic Route of 79432-87-4, A common heterocyclic compound, 79432-87-4, name is (E)-Methyl 3-(3-bromophenyl)acrylate, molecular formula is C10H9BrO2, 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 dry flask were added (E) -methyl 3- (3-bromophenyl) acrylate (1.18 g, 4.89 mmol) , methanol (10 mL) and 10%Pd/C (120 mg) in turn, the mixture was stirred at 40 under H2for 6 hours. The mixture was filtered and the filtrate was concentrated in a rotary evaporator to get the title compound as a brown liquid (1.2 g, 100%) . ESI: (ESI, pos. ion) m/z: 243.1 [M+H]+.

The synthetic route of 79432-87-4 has been constantly updated, and we look forward to future research findings.

Reference:
Patent; SUNSHINE LAKE PHARMA CO., LTD.; LIU, Xinchang; REN, Qingyun; YAN, Guanghua; GOLDMANN, Siegfried; ZHANG, Yingjun; (253 pag.)WO2019/76310; (2019); A1;,
Ester – Wikipedia,
Ester – an overview | ScienceDirect Topics

Related Products of 636-53-3, These common heterocyclic compound, 636-53-3, name is Diethyl isophthalate, 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.

Will 6.8Kg of diethyl isophthalate, 24.0 kg of 2,2,6,6-tetramethyl-4-aminopiperidine was added to a 50 liter reactorIn the reactor all the materials off the entrance. The reaction was carried out at 190 C for 2 hours and then at 230 C for 6 hours. The temperature was lowered to below 180 C, and excess 2,2,6,6-tetramethyl-4-aminopiperidine was recovered by vacuum distillation under a vacuum pump. Then use water to generateN, N’-bis (2,2,6,6-tetramethyl-4-piperidinyl) -1,3-benzenedicarboxamide, filtered and dried to give 12.4 kg of acicular white crystalline product , Yield 91.6%.

Statistics shows that Diethyl isophthalate is playing an increasingly important role. we look forward to future research findings about 636-53-3.

Reference:
Patent; Xiangtan University; Luo Zhiqiang; Zhang Lingjun; Zhang Jing; Ji Yongsheng; Ji Changfu; Zeng Yang; Liu Mengyan; Zhou Ji; Liu Minna; Wang Zhe; (7 pag.)CN106905225; (2017); A;,
Ester – Wikipedia,
Ester – an overview | ScienceDirect Topics

Reference of 25081-39-4, 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. 25081-39-4, name is Methyl 3,5-dimethylbenzoate belongs to esters-buliding-blocks compound, it is a common compound, a new synthetic route is introduced below.

Step CC: (R)-3-(3,5-dimethylbenzoyl)-4-methyldihydrofuran-2-one To a solution of (R)-4-methyldihydrofuran-2-one (1.68 g in 40 mL dioxane) were added 5.51 g 3,5-dimethylbenzoic acid methyl ester followed by 1.82 g sodium hydroxide and the mixture heated to reflux on an oil bath. After 3 hours, the mixture was cooled to room temperature and the pH neutralized by the addition of 0.5N hydrochloric acid. The mixture was then extracted with ethyl acetate and the organic portion washed with brine and dried over sodium sulfate. Purification of the concentrate by flash chromatography on silica gel (hexane:ethyl acetate, 9:1) gave the title compound (2.42 g).

The synthetic route of Methyl 3,5-dimethylbenzoate has been constantly updated, and we look forward to future research findings.

Reference:
Patent; Merck & Co., Inc.; US6017944; (2000); A;; ; Patent; Merck & Co., Inc.; US6159975; (2000); A;; ; Patent; Merck & Co., Inc.; US5985901; (1999); A;,
Ester – Wikipedia,
Ester – an overview | ScienceDirect Topics