Esters-buliding-blocks

73792-08-2, These common heterocyclic compound, 73792-08-2, name is Methyl 4-amino-2-fluorobenzoate, 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 solution of the compound of Reference Example 11-1 (358 mg, 1.20 mmol) in dichloromethane (4 mL), oxalyl chloride (113 muL, 1.32 mmol) and DMF (5 muL) were added at 0C, and the mixture was stirred for 20 minutes. To the reaction solution, a solution of methyl 4-amino-2-fluorobenzoate (105.4 mg, 0.623 mmol) and diisopropylethylamine (310 muL, 1.80 mmol) in dichloromethane (2 mL) was added at 0C, and the mixture was stirred for 2 hours. A saturated aqueous solution of ammonium chloride was added to the reaction mixture, followed by extraction with ethyl acetate. The organic layer was washed with a saturated saline solution, then dried over magnesium sulfate and filtered, and the filtrate was concentrated under reduced pressure. The obtained residue was purified by silica gel column chromatography to obtain the title compound (83.2 mg, 30%). MS (ESI+) 449 (M+1, 84%)

Chemical properties determine the actual use. Each compound has specific chemical properties and uses. We look forward to more synthetic routes in the future to expand reaction routes of 73792-08-2.

Reference:
Patent; Sumitomo Dainippon Pharma Co., Ltd.; IKUMA Yohei; FUKUDA Nobuhisa; IWATA Masato; KIMURA Hidenori; SUZUKI Kuniko; EP2876105; (2015); A1;,
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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. 23680-40-2 name is Methyl 3-bromopropiolate, 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. 23680-40-2

Reaction Step 2. Synthesis of 7-tert-butyl 2-ethyl 3-bromo-7-azabicyclo[2.2.1]hepta-2,5-diene-2,7-dicarboxylateA mixture of methyl 3-bromopropiolate (5.00 g, 28.2 mmol, 1.0 eq) and tert-butyl 1H-pyrrole-1-carboxylate (14.00 g, 84.7 mmol, 3.0 eq) in a sealed tube was heated to 90 C. for 14 h. After completion of the reaction (monitored by TLC, 5% ethyl acetate-hexane Rf=0.3), The reaction mixture was purified without work up by flash column chromatography on silica gel (100-200 mesh), eluting with 5% ethyl acetate in hexanes to afford 7-tert-butyl 2-methyl 3-bromo-7-azabicyclo[2.2.1]hepta-2,5-diene-2,7-dicarboxylate (2.0 g, 20%) as a brown oil. LCMS m/z=344.2 (M+1); purity=75%.

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

Reference:
Patent; INNOV17 LLC; Gaweco, Anderson; Tilley, Jefferson; Blinn, James; US2015/252051; (2015); A1;,
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2065-23-8, 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. 2065-23-8, name is Methyl 2-phenoxyacetate, A new synthetic method of this compound is introduced below.

REFERENCE EXAMPLE 90 Dimethyl 2-oxo-3-phenoxy-propylphosphonate 90 STR109 Dimethyl methylphosphonate (18 ml, 0.166 mol) was addded to anhydrous THF (150 ml) under argon atmosphere and cooled to -78 C. After 20 min. a solution of n-butyl lithium in hexane (1.59N, 108.8 ml, 0.173 mmol) was added to the mixture. After being stirred for 30 min. a solution of methyl phenoxyacetate (10 ml, 0.069 mmol) in 10 ml of anhydrous THF was added, and the reaction mixture was stirred successively for 30 min. at -78 C. and for 30 min. at room temperature, and acidified with acetic acid. After confirming a weakly acidic pH of the solution thus obtained, THF was distilled out. Water (50 ml) was added to the residue, and the resulting mixture was extracted with ethyl acetate (150 ml*3). The combined organic layers were washed with 100 ml of water and with 100 ml of brine, dried over anhydrous sodium sulfate, and concentrated. The oily product was distilled under reduced pressure to afford dimethyl 2-oxo-3-phenoxypropylphosphonate (14.65 g, 0.057 mol, yield: 82.3%). B.p.: 145-147 C./0.1 mmHg. The product was identified by the following data. IR(liquid film): 3450, 3070, 3025, 2960, 2920, 2860, 1740, 1605, 1595, 1495, 1460, 1430, 1405, 1370, e1300, 1250, 1230, 1180, 1160, 1100, 1030, 890, 830, 810, 800 cm-1. NMR(90 MHz, CDCl3, delta): 3.27(2H, d, J=22.7 Hz); 3.77(6H, d, J=11.2 Hz); 4.69(2H, s); 6.84-7.38 (5H, m).

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; Toray Industries, Inc.; US4775692; (1988); A;,
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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 59833-69-1 as follows. 59833-69-1

General procedure: To a stirred solution of 12e (62 mg, 0.4 mmol) in CH2Cl2 (5 mL) were added a solution of 18 (133 mg, 0.4 mmol) in CH2Cl2 (3 mL) and then pyridine (0.067 mL, 0.8 mmol). After stirring overnight at room temperature, the reaction mixture was diluted with water and extracted with EtOAc (¡Á2). The combined organic layers were washed with 1 M NaOH aq, water, brine, dried over Na2SO4 and concentrated in vacuo. The resulting residue was purified by column chromatography on silica gel to yield methyl ester (120 mg, 63%); TLC Rf = 0.14 (n-hexane/EtOAc, 7:3); 1H NMR (300 MHz, CDCl3) delta 7.60-7.38 (m, 4H), 7.32 (t, J = 7.8 Hz, 1H), 7.06 (d, J = 7.5 Hz, 1H), 6.92-6.77 (m, 4H), 6.74-6.66 (m, 2H), 4.70-4.60 (m, 1H), 4.26 (dd, J = 9.6, 5.4 Hz, 1H), 4.14 (dd, J = 11.4, 6.6 Hz, 1H), 3.71 (s, 3H), 3.65 (s, 2H), 3.39 (dd, J = 11.4, 3.0 Hz, 1H), 3.26 (dd, J = 11.4, 7.8 Hz, 1H), 2.91 (s, 3H), 2.51 (s, 3H).CommentTo a stirred solution of methyl ester (120 mg, 0.25 mmol) described above in MeOH (4 mL) and THF (4 mL) was added 5 M NaOH aq (2 mL). After stirring for 1 h at room temperature, the reaction mixture was diluted with 2 M HCl aq and extracted with EtOAc (¡Á2). The combined organic layers were washed with water, brine, dried over Na2SO4 and concentrated in vacuo to give a crude product, which was washed with EtOAc/n-hexane to yield 4a (85 mg, 73%) as a pale blue powder

According to the analysis of related databases, 59833-69-1, the application of this compound in the production field has become more and more popular.

Reference:
Article; Iwahashi, Maki; Takahashi, Eiji; Tanaka, Motoyuki; Matsunaga, Yoko; Okada, Yutaka; Matsumoto, Ryoji; Nambu, Fumio; Nakai, Hisao; Toda, Masaaki; Bioorganic and Medicinal Chemistry; vol. 19; 18; (2011); p. 5361 – 5371;,
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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. 36692-49-6, name is Methyl 3,4-diaminobenzoate belongs to esters-buliding-blocks compound, it is a common compound, a new synthetic route is introduced below. 36692-49-6

Step 450b. The mixture of (S)-1-(tert-butoxycarbonyl)pyrrolidine-2-carboxylic acid (5 g, 23.2 mmol) in acetonitrile (40 mL) was added 1,1?-carbonyldiimidazole (3.95 g, 24.5 mmol). The resulting mixture was stirred at room temperature for 20 min before being added methyl 3,4-diaminobenzoate (3.86g, 23.2 mmol). The solution was stirred at room temperature for another 3 hours before being partitioned between water and EtOAc. The organic phase was separated, dried (Na2SO4) and concentrated to afford a brown slurry, which was purified by flash column chromatography (silica, hexane-EtOAc) to give the desired product as a light yellow oil (8.14g, 98%). ESIMS m/z=364.17 [M+H]+. ; Step 450c. The solution of compound from step 450b in acetic acid (150 mL) was stirred at 60 C. for three days before all volatiles were removed. The resulting residue was partitioned between aqueous NaHCO3 and EtOAc. The organic phase was separated, dried (Na2SO4) and concentrated to afford a brown oil, which was purified by flash column chromatography (silica, hexane-EtOAc) to give the desired product as a light yellow solid (2.02 g, 28%). ESIMS m/z=346.15 [M+H]+.

The synthetic route of 36692-49-6 has been constantly updated, and we look forward to future research findings.

Reference:
Patent; Enanta Pharmaceuticals, Inc.; Qiu, Yao-Ling; Wang, Ce; Peng, Xiaowen; Ying, Lu; Or, Yat Sun; US2020/2314; (2020); A1;,
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Some common heterocyclic compound, 609-12-1, name is Ethyl 2-bromo-3-methylbutanoate, molecular formula is C7H13BrO2, 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. 609-12-1

General procedure: Benzenesulfonamide (1.2mmol), ethyl alpha-bromophenylacetate or ethyl pheny-lacetate (2.4mmol), and toluene (4mL)werecombinedinasealedtubeequippedwith astirbar.Themixturewasstirredat50Cfor10min,TiCl4 (1.8 mmol) was added, andthereactionmixturewasheatedto115C.Afteravariableperiodoftimethe mixturewasdilutedwithH2O (10mL)toremovetheexcessofTiCl4, filtered,andextracted withAcOEt(3¡Á15mL). The combined organic layers were dried over anhydrous Na2SO4 and thesolventwasevaporatedinvacuo.Crudecompoundswere purified by flash column chromatography (silicagel;cyclohexane=AcOEt 8:2). 2-Bromo-N-[(4-methoxyphenyl)sulfonyl]-3-methylbutanamide (4c). Sticky oil, 59% yield; IR(KBr) 3564, 3236, 2970, 1906, 1722, 1596, 1499, 1443, 1346, 1265, 1165, 1087, 1023, 865, 834,559 cm-1; 1H NMR (CDCl3) d 0.94 (d, 3H, J 6.3Hz, CH3), 0.95 (d, 3H, J 6.6 Hz, CH3), 2.19(octuplet, 1H, J 6.6 Hz, CH3CHCH3), 3.87 (s, 3H, OCH3), 4.09 (d, 1H, J 6.6 Hz, CHBr), 6.99 (d,2H, J 9.0 Hz, CH Ar), 8.00 (d, 2H, J 9.6 Hz, CH Ar), 9.09 (broad s, 1H, NH); 13C NMR (CDCl3)d 18.9 and 20.2 (CH3), 32.4 (CH3CHCH3), 55.7 (OCH3), 58.0 (CHBr), 114.1 (CH Ar), 129.0 (CSAr), 130.9 (CH Ar), 164.1 (CH3OC Ar), 166.2 (CONH); Anal calcd for C12H16BrNO4S: C 41.15; H4.60; N 4.00; found C 41.22; H 4.59; N 4.02 %.

These compound has a wide range of applications. It is believed that with the continuous development of the source of the synthetic route 609-12-1, its application will become more common.

Reference:
Article; Ammazzalorso, Alessandra; Tricca, Maria Luisa; Bruno, Isabella; De Filippis, Barbara; Di Matteo, Mauro; Fantacuzzi, Marialuigia; Giampietro, Letizia; Maccallini, Cristina; Mollica, Adriano; Amoroso, Rosa; Synthetic Communications; vol. 45; 22; (2015); p. 2546 – 2554;,
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The chemical industry reduces the impact on the environment during synthesis 13671-00-6, name is Methyl 2,6-difluorobenzoate, I believe this compound will play a more active role in future production and life. 13671-00-6

1,8-Diazabicyclo[5.4.0]undec-7-ene (0.43 ml, 2.90 mmol, 5.0 eq) wasadded to a solution of methyl 2,6-difluorobenzoate (100 mg, 0.58 mmol, 1.0 eq) in methanol (0.35 mL). The resulting solutionwas stirred at room temperature and hydroxylamine in aqueous solution 50% (0.36ml, 5.81 mmol, 10.0 eq) was added. After 2h the reaction was stopped and themixture is adjusted to pH 6 with acetic acid. The aqueous layer was extractedthree times with ethyl acetate. The combined organic layer was dried with MgSO4,concentrated and purified by preparative HPLC to afford 2,6-difluoro-N-hydroxy-benzamide (54 mg, 0.31 mmol, 54 %) as a white solid: MS ES+ m/z 174.1 (M+H)+; 1HNMR (400 MHz, DMSO-d6) delta 11.18 (s, 1H), 9.41 (s, 1H), 7.54 (m, 1H), 7.22 – 7.14 (m, 2H); 13CNMR (101 MHz, DMSO-d6) delta 159.3 (dd, J = 249.9, J = 8.4 Hz), 156.6, 132.2 (t, J = 10.3 Hz), 113.3 (t, J = 23.3 Hz), 112.1 (dd, J = 19.7, J = 5.4 Hz) ; 19FNMR (377 MHz, DMSO-d6) delta -113.6 (t, J = 7.0 Hz).

The chemical industry reduces the impact on the environment during synthesis 13671-00-6. I believe this compound will play a more active role in future production and life.

Reference:
Article; Beillard, Audrey; Bhurruth-Alcor, Yushma; Bouix-Peter, Claire; Bouquet, Karinne; Chambon, Sandrine; Clary, Laurence; Harris, Craig S.; Millois, Corinne; Mouis, Gregoire; Ouvry, Gilles; Pierre, Romain; Reitz, Arnaud; Tomas, Loic; Tetrahedron Letters; vol. 57; 20; (2016); p. 2165 – 2170;,
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6279-86-3, These common heterocyclic compound, 6279-86-3, name is Triethyl methanetricarboxylate, 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.

10 g 3-Amino-5,5-dimethyl-2-cyclohexen-1-one and 25 g 2-Ethoxycarbonyl-malonic acid diethyl ester are combined and heated for 10 minutes at 210 C. (bath temperature). Thereafter the mixture is cooled to room temperature and triturated with diethylether. The crystalline precipitate is collected by filtration and dried in vacuo.Yield: 9.9 g (49% of theory)Mass spectrometry (ESI+): m/z=280 [M+H]+ Rf-value: 0.45 (silica gel, dichloromethane/methanol 9:1)

Chemical properties determine the actual use. Each compound has specific chemical properties and uses. We look forward to more synthetic routes in the future to expand reaction routes of 6279-86-3.

Reference:
Patent; BOEHRINGER INGELHEIM INTERNATIONAL GMBH; US2012/46304; (2012); A1;,
Ester – Wikipedia,
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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. 6279-86-3, name is Triethyl methanetricarboxylate, This compound has unique chemical properties. The synthetic route is as follows., 6279-86-3

Synthesis of sodium salt of 2-ethoxycarbonyl-malonic acid diethyl ester; Sodium ethoxide solution was prepared in a flame-dried 100 mL flask under a flow of argon gas using sodium metal (0.21 g, 9.14 mmol) and dry ethanol and was added slowly to a solution of triethyl methanetricarboxylate (2.12 g, 9.14 mmol) in 20 mL of THF while the reaction temperature was maintained around 1 0C using an ice bath. This resulted in the precipitation of product as white solid. The solvent was removed under reduced pressure and the salt was washed with dry petroleum ether and dried under high vacuum to get the product, which was non-hygroscopic in nature. 1H NMR (300 MHz, D2O): 1.22 (t, 9H), 4.08 (q, 6H). Mass: 232 [(MM)-Na+].

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; INDIAN INSTITUTE OF TECHNOLOGY BOMBAY; WO2006/117800; (2006); A2;,
Ester – Wikipedia,
Ester – an overview | ScienceDirect Topics

37466-90-3, Name is Ethyl 3,4-diaminobenzoate, 37466-90-3, belongs to esters-buliding-blocks compound, is considered to be a conventional heterocyclic compound, which is widely used in drug synthesis. The chemical synthesis route is as follows.

General procedure: Ethyl-3-amino-4-(2-substituted amino)benzoate, 3 (1 mmol) and various sodium bisulfite adducts, 4 (1.5 mmol) were dissolved in DMF (5 mL). The reaction mixture was stirred at 90 C under N2 atmosphere for 24-48 h. After completion of reaction (evident by TLC), the reaction mixture was diluted in ethyl acetate (25 mL) and washed with water (10 mL¡Á3). The organic layer was collected, dried over Na2SO4 and evaporated under reduced pressure to afford crude products. Final compounds 5-7 were obtained in 38-90% yields after recrystallization from ethanol or column purification.

Statistics shows that Ethyl 3,4-diaminobenzoate is playing an increasingly important role. we look forward to future research findings about 37466-90-3.

Reference:
Article; Yoon, Yeong Keng; Ali, Mohamed Ashraf; Wei, Ang Chee; Choon, Tan Soo; Ismail, Rusli; European Journal of Medicinal Chemistry; vol. 93; (2015); p. 614 – 624;,
Ester – Wikipedia,
Ester – an overview | ScienceDirect Topics