Month: June 2021

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;,
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Related Products of 13831-03-3, 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 13831-03-3 as follows.

To the mixture of methyl 3-iodobenzoate (157 mg, 0.60 mmol), K2CO3 (166 mg, 1.20 mmol), cupper(I) iodide (14 mg, 0.07 mmol) and PdCl2(Ph3P)2 (21 mg, 0.03 mmol) in tetrahydrofuran (2 mL) was added tert-butyl propiolate (16) (330 mL, 2.40 mmol) at room temperature. After stirred for 20 h at 60C, the mixture was evaporated to dryness. The residue was chromatographed on a silica gel (AcOEt:hexanes=0:1~1:10) to give tert-butyl 3-(3-(methoxycarbonyl)phenyl)propiolate (17b) (155 mg, 99% yield) as light brown oil. 1H NMR (300 MHz, CDCl3) delta 8.25 (t, J = 1.4, 1H), 8.16 – 8.05 (m, 1H), 7.80 – 7.68 (m, 1H), 7.46 (t, J = 7.8, 1H), 3.93 (s, 3H), 1.55 (s, 9H).

According to the analysis of related databases, 13831-03-3, the application of this compound in the production field has become more and more popular.

Reference:
Article; Kawate, Tomohiko; Iwase, Noriaki; Shimizu, Motohisa; Stanley, Sarah A.; Wellington, Samantha; Kazyanskaya, Edward; Hung, Deborah T.; Bioorganic and Medicinal Chemistry Letters; vol. 23; 22; (2013); p. 6052 – 6059;,
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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;,
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Electric Literature of 24812-90-6, These common heterocyclic compound, 24812-90-6, name is Methyl 3-amino-4-methoxybenzoate, 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.

Anhydrous p-toluene sulfonic acid (20.99 g, 110.04 mmol) was melted at 120 C and 3-amino-4-methoxy benzoic acid methyl ester (10 g, 55.20 mmol) obtained in step 1 of Preparation Example 1 and 2,4-dichlorobenzonitrile (18.99 g, 110.04 mol) were added thereto and stirred at 180 C for 6 hours. The resulting solution was cooled to room temperature and the reaction was stopped by adding NaHCO3 thereto. The resulting mixture was extracted with ethyl acetate, the extract was dried over MgSO4 and concentrated under a reduced pressure. The concentrate was dissolved in 50 % methanol and 5 % NaOCl (30 ml, 20.64 mmol) was added dropwise thereto. After 5 min, the resulting mixture was extracted with ethyl acetate, the extract was dried over MgSO4 and concentrated under a reduced pressure. The resulting residue was purified by silica gel column chromatography (eluent-MeOH/CDCl3=5:95, Merck, Silicagel 60) to obtain the title compound (18 g, 10.32 mmol) in a yield of 84 %. 1H NMR (CDCl3): delta 8.23 (1H, br), 7.75 (1H, d), 7.44 (1H, d), 7.36-7.26 (2H, m), 7.03 (1H, s), 6.88 (1H, d), 3.96 (3H, s), 3.76 (3H, s) MW: 318

Statistics shows that Methyl 3-amino-4-methoxybenzoate is playing an increasingly important role. we look forward to future research findings about 24812-90-6.

Reference:
Patent; CRYSTALGENOMICS, INC.; YUYU INC.; WO2004/65370; (2004); A1;,
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Reference of 394-35-4, A common heterocyclic compound, 394-35-4, name is Methyl 2-fluorobenzoate, molecular formula is C8H7FO2, 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 reactor under nitrogen atmosphere was added a toluene solution of ester 6 (LOO Wt, 1.0 eq), methyl 2-fluorobenzoate (0.91 Wt, 0.75 Vol 1.10 eq)5 and THF (0.53 Wt, 1.8 Vol). The solution was cooled to below -70 C. Lithium hexamethyldisilazide (LiHMDS, 1.0M in THF, 7.6 Wt, 8.6 Vol, 1,6 eq) was added at such rate that the internal temperature does not exceed -60°C.. After completion of the LiHMDS addition, the mixture was warmed (rate between 10-20C/h) and stirred at -40C for 1h. The reaction was monitored by GC (Conversion Target >95percent). If after 4h the conversion is still under targeted amount, additional LiHMDS 1M in THF was added (1.1 eq based on unreacted starting material). After achieving the target conversion, the internal temperature was raised (rate between 20-30°C/h) to 15 to 20 °C. 25 wtpercent aqueous ammonium chloride (1,7 Wt, 1.6 Vol) was added to the reactor keeping the internal temperature below 0 °C Upon completion of the addition, the mixture was warmed to ?0°C, and transferred to a vessel containing 25 wtpercent aqueous ammonium chloride (4.4 Wt, 4.1 Vol) and water (1.1 Wt, 1.1 Vol).The mixture was stirred for at least 30 min at 20-25 °C. The lower aqueous layer was removedand the organic layer was washed with 20 wt percent aqueous sodium chloride (3.0 Wt, 1.4 Vol). The mixture was stirred for at least 15 minutes then allowed to settle. The lower aqueous layer was removed. The organic phase was concentrated under reduce pressure (Jacket < 25 °C) untildistillation ceases. Toluene (6.6 Wt, 6.7 Vol) was added and the resulting mixture was washedwith water (3.0 Wt, 3.0 Vol), stirred for at least 15 min, then allowed to settle. The organics werewashed with water (3.0 Wt, 3.0 Vol) until pH is constant at pH=78. The organic phase was washed with 20percent aqueous sodium chloride (3.0 Wt, 1.4 Vol). The organic phase was concentrated under reduced pressure (jacket <25°C) to afford ketoester 11 (2.1 Wt) as an orangeoil. The synthetic route of 394-35-4 has been constantly updated, and we look forward to future research findings. Reference:
Patent; ???????????????????????????; ? Buranko; Kimu ?; Chan ?; ?; Yoshizawa Kazuhiro; (94 pag.)JP2016/121177; (2016); A;,
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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. 40637-56-7, name is Dimethyl 2-allylmalonate belongs to esters-buliding-blocks compound, it is a common compound, a new synthetic route is introduced below. Product Details of 40637-56-7

According to a reported procedure,18 a solution of dimethyl 2-allylmalonate (19) (1.77 mL, 11.0mmol, 1.0 equiv) in Et2O (25 mL) was added dropwise to a suspension of LiAlH4 (1.25 g, 33.0mmol, 3.0 equiv) in Et2O (31 mL) at 0C. The resulting mixture was stirred at room temperature for3 h; it was then cooled back to 0C and the reaction was quenched by slow addition of water (1.05mL). The mixture was allowed to warm to rt and treated with aqueous NaOH (15%, 1.05 mL) andwater (3.2 mL). The resulting white slurry was filtered through Celite and then washed with EtOAc(4 x 50 mL). After removal of the solvent by distillation under reduced pressure, the crude productwas purified by column chromatography (SiO2, eluting with Et2O) to afford diol 20 as a colorlessoil (744 mg, 6.40 mmol, 58% yield). Following a reported procedure,19 a solution of diol 20 (581 mg, 5.00 mmol, 1.0 equiv) in THF (4.0mL) was added dropwise to a suspension of NaH (60% dispersion in mineral oil, 120 mg, 5.00mmol, 1.0 equiv) in THF (10 mL). The mixture was stirred at rt for 50 min and then a solution oftriisopropyl silyl chloride (0.96 mL, 4.5 mmol, 0.9 equiv) in THF (4.0 mL) was slowly added. Afterstirring for 2 h, the reaction was quenched by treatment with aqueous K2CO3 (1.0 M, 15 mL). Theaqueous layer was separated from the organic one and extracted with Et2O (3 x 15 mL). Thecombined organic layers were washed with brine (15 mL), dried over MgSO4, filtered and thesolvent was removed in vacuo. Purification by column chromatography (SiO2, eluting with 95:5pentane:EtOAc) afforded the monoprotected diol 21 as a colorless oil (1.15 g, 4.23 mmol, 85%yield).

The synthetic route of 40637-56-7 has been constantly updated, and we look forward to future research findings.

Reference:
Article; Nicolai, Stefano; Swallow, Peter; Waser, Jerome; Tetrahedron; vol. 71; 35; (2015); p. 5959 – 5964;,
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Adding a certain compound to certain chemical reactions, such as: 4891-38-7, name is Methyl Phenylpropiolate, 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 4891-38-7, COA of Formula: C10H8O2

General procedure: A reaction kettle (30 mL) was charged with aniline (1.0 mmol), and alkyne ester (1.0 mmol). The mixture was stirred at room temperature for 10 minutes, then added terminal alkyne (1.2 mmol, 1.2 eq), AgOTf (5 mol%, 12.9 mg), HOTf (10 mol%, 15 mg), MeOH (2 mL) in the mixture. The mixture was stirred at 120 oC for 24 hours, the mixture was quenched by sat. aq. NaHCO3, and diluted with 20 mL of dichloromethane and washed with 10 mL of H2O. The aqueous layer was extracted twice with dichloromethane (10 mL) and the combined organic phase was dried over Na2SO4. After evaporation of the solvents, the residue was purified by silica gel chromatography (hexane/AcOEt = 5:1) to afford quinoline derivatives. All other compounds are synthesized in a similar manner, with the yields listed in the main text calculated from the isolated, pure products.

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

Reference:
Article; Li, Yunlan; Zhang, Qiurui; Xu, Xuefeng; Zhang, Xu; Yang, Yurong; Yi, Wei; Tetrahedron Letters; vol. 60; 14; (2019); p. 965 – 970;,
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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. 90971-88-3, name is Methyl 2-bromo-5-methylbenzoate belongs to esters-buliding-blocks compound, it is a common compound, a new synthetic route is introduced below. Safety of Methyl 2-bromo-5-methylbenzoate

Example 15; Synthesis of 5-methyl-2-triisopropylsilanylsulfanyl-benzoic acid methyl ester (Method 15.) 2-Bromo-5-methyl-benzoic acid methyl ester (2.06 g, 9.00 mmol), tris(dibenzylideneacetone)dipalladium (0) (83 mg, 0.09 mmol), bis(2-diphenylphosphinophenyl)ether (97 mg, 0.18 mmol), sodium tert-butoxide (1.00 g, 10.4 mmol), triisopropylsilanethiol (1.37g, 7.2 mmol) and dry toluene (10 mL) are all placed in an Emrys Optimizer EXP 20 mL microwave reactor tube. The reaction vessel is sealed and subjected to microwave heating at 150 C. for 30 minutes. Upon cooling the mixture is poured onto a plug of silica and the product is eluted with ethyl acetate-heptane (2:8). This furnishes the title compound as an oil, which is used in the next step without further purification.

The synthetic route of 90971-88-3 has been constantly updated, and we look forward to future research findings.

Reference:
Patent; Kehler, Jan; Juhl, Karsten; Norgaard, Morten Bang; US2006/287386; (2006); A1;,
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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. 18595-14-7, name is Methyl 4-amino-3-methylbenzoate, This compound has unique chemical properties. The synthetic route is as follows., Product Details of 18595-14-7

Into a 500-mL round-bottom flask was placed a solution of methyl 4-amino-3-methylbenzoate (4.00 g, 24.2 mmol, 1.00 equiv) and NaSCN (7.00 g, 86.4 mol, 3.57 equiv) in AcOH (90 mL) that was cooled to 0 C. This was followed by the addition of a solution of Br2 (3.9 g, 25 mmol, 1.0 equiv) in AcOH (25 mL) dropwise, maintaining at 0 C over 20 min. The resulting solution was allowed to warm to RT on its own accord (over approximately 10 min.) and stirred for 48 hrs at RT. At this time, the solids of the reaction were filtered out. The resulting solution was diluted with 100 mL H20. The pH value of the solution was adjusted to 8-9 with ammonia (using Whatman PH strip paper to monitor PH adjustment) which furnished an immediate precipitation. The solids were collected by filtration and washed once with ice cold MeOH (50 mL) to afford as a yellow solid. MS m/z 223.0 (M+l). 1H NMR (400 MHz, MeOH- 4) delta 8.17 (app d, J = 1.0 Hz, 1H), 8.03 (br s, 2H, NH2), 7.68 (s, 1H), 3.82 (s, 3H), 2.42 (s, 3H).

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; IRM LLC; TULLY, David C.; RUCKER, Paul Vincent; ALPER, Phillip B.; MUTNICK, Daniel; CHIANELLI, Donatella; WO2012/87519; (2012); A1;,
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Application of 924-99-2,Some common heterocyclic compound, 924-99-2, name is Ethyl 3-(dimethylamino)acrylate, molecular formula is C7H13NO2, 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 solution of MeCN (1 mmol) containing chromene diene 13 (0.5 mmol) and the corresponding enamino ester 9 or? -enaminokone 11 (0.6 mmol) shown in Table 1 3.0 mL) was stirred at room temperature while adding indium (III) trifluoromethanesulfonate [Indium (III) trifluoromethanesulfonate].The reaction mixture was stirred for 2-8 hours, and after completion of the reaction was confirmed by TLC (hexane-EtOAc, 4: 1, v / v), 10 mL of water was added and the solution was extracted with ethyl acetate (10 mL x 3) .The solvent was evaporated and the residue was subjected to silica gel column chromatography using hexane-ethyl acetate (4: 1, v / v) to obtain the following compound.

These compound has a wide range of applications. It is believed that with the continuous development of the source of the synthetic route Ethyl 3-(dimethylamino)acrylate, its application will become more common.

Reference:
Patent; Yeungnam University Industry-Academic Cooperation Foundation; Lee Yong-rok; (31 pag.)KR2018/3669; (2018); A;,
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