Month: January 2021

Adding a certain compound to certain chemical reactions, such as: 18595-12-5, name is Methyl 5-amino-2-methylbenzoate, 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 18595-12-5, HPLC of Formula: C9H11NO2

Methyl 5-amino-2-methylbenzoate (1.0 eq, 3.75 g) was dissolved in acetic acid (70 ml). N-Iodosuccinimide (1.0 eq, 5.27 g) was added portionwise over 60 minutes. The mixture was stirred at room temperature for 30 minutes. Acetic acid was evaporated. The residue was diluted with ethyl acetate (80 ml) and neutralized with saturated sodium carbonate (80 ml). The organic layer was washed with 1M sodium thiosulfate (2¡Á40 ml), then water (2¡Á40 ml) and brine (2¡Á40 ml). The material was purified by flash chromatography on silica gel (gradient 10% to 30% ethyl acetate in hexanes) to provide methyl 5-amino-4-iodo-2-methylbenzoate as a yellow-orange solid (3.19 g, 49% yield). GCMS>95% pure, m/z 291. 1H NMR (400 MHz, DMSO, d6) delta 2.30 (s, 3H), 3.78 (s, 3H), 5.27 (br s, 2H), 7.24 (s, 1H), 7.54 (s, 1H).

At the same time, in my other blogs, there are other synthetic methods of this type of compound, Methyl 5-amino-2-methylbenzoate, and friends who are interested can also refer to it.

Reference:
Patent; CHUA, Peter C.; Haddach, Mustapha; Nagasawa, Johnny Y.; Pierre, Fabrice; Whitten, Jeffrey P.; US2009/239859; (2009); A1;,
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Related Products of 15441-07-3,Some common heterocyclic compound, 15441-07-3, name is Methyl 3-(chlorosulfonyl)propanoate, molecular formula is C4H7ClO4S, 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 14 N-isobutyl-3-amidosulfopropionic Acid To 14.6 parts of isobutylamine and 100 parts of water there are added dropwise at 0 C, with stirring 18.65 parts of methyl 3-chlorosulfonylpropionate and then simultaneously from separate dropping funnels 18.65 parts of methyl 3-chlorosulfonylpropionate and 54 parts of 14.8% caustic soda solution. Stirring is continued for a further hour at 0 C and 4 hours at room temperature; 8.8 parts of sodium hydroxide are added and the mixture is heated at 60 C for 4 hours. The reaction mixture is acidified with a 2N H2 SO4 solution to a pH of 1 and the resulting precipitate is filtered off, washed with 100 parts of water and dried at 40 C/25 mm. Yield: 24.6 parts (59% of theory) of white crystalline N-isobutyl-3-amidosulfopropionic acid, m.p. 132-134 C (after recrystallization from H2 O).

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

Reference:
Patent; BASF Aktiengesellschaft; US4060522; (1977); A;,
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These common heterocyclic compound, 110661-91-1, name is tert-Butyl 4-bromobutanoate, 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. Product Details of 110661-91-1

General procedure: To 100 mLrbf was added a mixture of compound 20 (1.66 g, 10 mmol), cesiumcarbonate (3.26 g, 10 mmol), TBAI (3.70 g, 10 mmol) and anhydrousDMF (20 mL). Compound 19 (2.23 g, 10 mmol) was added dropwise tothe mixture. The reaction mixture was then stirred at room temperaturefor 3 h. Ethyl acetate was added into the reaction mixture. The combinedmixture was washed with two portions of water. After evaporationof the solvent under reduced pressure MeOH (20 mL) was addedfollowed by silica gel (1 g). The resulting plug was loaded on to a silicagel column and eluted with 1:10 (ethyl acetate: hexane). Fractions withand Rf = 0.64 (hexane:ethyl acetate 1:1) were pooled and evaporatedto afford tert-butyl esters (1.47 g, yield; 47%). Trifluoroacetic acid wasthen added into the tert-butyl esters and mixture was stirred at roomtemperature for 30 min. Excess of trifluoroacetic acid was evaporatedand MeOH (20 mL) was added followed by silica gel (1 g). The resultingplug was loaded on to a silica gel column and eluted with 1:10 (ethylacetate: hexane). Fractions with and Rf = 0.45 (TLC) (Hexane: ethylacetate,1:1) were pooled and evaporated to afford 22 (1 g, yield 83%)as white solid.

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

Reference:
Article; Dekhne, Aamod S.; Gangjee, Aleem; Golani, Lalit K.; Hou, Zhanjun; Islam, Farhana; Matherly, Larry H.; O’Connor, Carrie; Bioorganic and medicinal chemistry; vol. 28; 12; (2020);,
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Reference of 89-91-8, These common heterocyclic compound, 89-91-8, name is Methyl 2,2-dimethoxyacetate, 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.

General procedure: A mixture of the appropriate nitrile (4, 2 mmol), hydroxylamine50% (0.132 g, 2 mmol), and a catalytic amount of AcOH was stirredat 150 C for 40 min. After nearly complete conversion to thecorresponding amidoxime, as was indicated by TLC monitoring, theappropriate 2,2-dialkoxyacetate (6, 2 mmol) and K2CO3 (0.276 g,2 mmol) were added to the reaction mixture which was stirred at100 C for further 6 h. After completion of the reaction as indicatedby TLC, the reaction mixture was cooled to room temperature andthe residue was purified by column chromatography using n-hexane-EtOAc (6:1) as eluent. The solvent was removed, and the product was obtained.

Statistics shows that Methyl 2,2-dimethoxyacetate is playing an increasingly important role. we look forward to future research findings about 89-91-8.

Reference:
Article; Adib, Mehdi; Saeedi, Sara; Soheilizad, Mehdi; Bayanati, Maryam; Tajbakhsh, Mahmood; Amanlou, Massoud; Journal of Chemical Research; vol. 40; 5; (2016); p. 314 – 317;,
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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. 50893-36-2, name is 1-Chloroethyl ethyl carbonate, This compound has unique chemical properties. The synthetic route is as follows., HPLC of Formula: C5H9ClO3

Reference Example 19 To a mixture of 1-[(1R,2R)-2-(2,4-difluorophenyl)-2-hydroxy-1-methyl-3-(1H-1,2,4-triazol-1-yl)propyl]-3-[4-(1H-tetrazol-1-yl)phenyl]-2-imidazolidinone (0.61 g) and 1-chloroethyl ethyl carbonate (3.7 g) was added acetonitrile (1 ml), and the mixture was stirred for 38 hours at 95¡ã C. The reaction mixture was concentrated under reduced pressure. To the residue was added diisopropyl ether (10 ml), and the resulting powder was collected by filtration. The powder was subjected to ODS column chromatography (eluent: methanol/water=3/2). The elude was concentrated in vacuo. The residue was dissolved in water (10 ml), and lyophilized to give 1-[(2R,3R)-2-(2,4-difluorophenyl)-2-hydroxy-3-[2-oxo-3-[4-(1H-tetrazol-1-yl)phenyl]-1-imidazolidinyl]butyl]-4-[-1-(ethoxy-carbonyloxy)ethyl]-1H-1,2,4-triazolium chloride (Compound 7,90 mg) as a white powder. 1H-NMR(d6-DSMO) delta: 0.97(3H,d,J=7 Hz), 1.21,1.22(3H,t,J=7 Hz), 1.79,1.80(3H, d,J=6 Hz), 3.62-4.23(6H,m), 4.65-5.10(3H,m), 6.69-6.82(2H,m), 6.94-7.04(1H,m), 7.26-7.38(2H,m), 7.90(4H,s), 9.23(0.5H,s), 9.27(0.5H,s), 10.08(1H,s), 10.72(0.5H,s), 10.82(0.5H,s).

According to the analysis of related databases, 50893-36-2, the application of this compound in the production field has become more and more popular.

Reference:
Patent; Takeda Chemical Industries, Ltd.; US6583164; (2003); B1;,
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. 924-99-2, name is Ethyl 3-(dimethylamino)acrylate, A new synthetic method of this compound is introduced below., category: esters-buliding-blocks

Example 3Reaction with 4 Molecular Sieve245 g (1.71 mole) of N,N-dimethylamino-ethyl-acrylate, 183.3 g (1.71 mole) of 2-ethylpyridine, 1.5 L of toluene and 250 g of 4 molecular sieves (that are UOP type 4 beads purchased from the Fluka Company) were added sequentially to a 5-liter reaction vessel. Then, nitrogen was introduced to the reaction vessel, an operation temperature in the reaction vessel was lowered to -10 C. and N,N-dimethylamino-ethyl-acrylate, 2-ethylpyridine and toluene were stirred for 10 minutes. 252.2 g (1.71 mole) of 2,2-dichloro-acetyl-chloride was dissolved in 500 mL of toluene and titrated into the reaction vessel in 30 minutes and then stirred for 1.5 hours at 0 C. to allow a synthetic reaction to proceed. TLC was used to analyze if N,N-dimethylamino-ethyl-acrylate was consumed to determine if the synthetic reaction had reached an end point. Once the end point was reached, 2 L of deionized water was added to the reaction vessel and contents of the reaction vessel were stirred for 30 minutes. After being stirred, the contents immediately separated into two phases. Then, a water phase and the 4 molecular sieves were removed and toluene was removed by vacuum pump to obtain a crude product. Next, the crude product was stirred, washed twice with 1 L hexane respectively and filtered by centrifuge. After being filtered, the crude product was dried in a vacuum oven for 5 hours to obtain a white product being 4,4-dichloro-2-(dimethylamino)methylene-3-oxy-alkyl butyrate (395.7 g; yield: 91%; purity: 99.8% (as shown in FIG. 3); melting point: 68 C.). The structure of the product was analyzed by 1H-NMR, 13C-NMR and frustrated total internal reflection (FTIR), which are respectively shown in FIGS. 4, 5 and 6.The 4 molecular sieves were soaked in 1 L of isopropanol for 24 hours, then dried at 120 C. for 24 hours to obtain 245 g of 4 molecular sieves (recycling rate: 98%).

The synthetic route of 924-99-2 has been constantly updated, and we look forward to future research findings.

Reference:
Patent; UFC Corporation; US7601864; (2009); B1;,
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. 35180-01-9, name is Chloromethyl isopropyl carbonate, A new synthetic method of this compound is introduced below., Formula: C5H9ClO3

Tenofovir (60 g, 0.209 mol) was placed in a 500 ml four-necked flask.250 g of N-methylpyrrolidone, and triethylamine (62.3 g, 0.617 mol) was added with stirring.Additional tetrabutylammonium bromide (40.25 g, 0.125 mol) was added.Warming up to 50 C,At this temperature, chloromethyl isopropyl carbonate (63.5 g, 0.418 mol) was added dropwise.Investment,Keep warm for 5 to 10 hours,After the end of the heat preservation, after extracting twice with n-heptane 250 ml¡Á2, the water was separated into 480 g of purified water, and extracted three times with isopropyl acetate 240 g+120 g+120 g, and the isopropyl acetate solution was combined and washed twice with an aqueous solution of 180 g¡Á2. , concentrated to dryness under reduced pressure at 40 C, 60 g of isopropanol, 40 CConcentrated to dryness under reduced pressure, adding 100 g of isopropanol, heating and dissolving, cooling to -10 to -20 C, adding 0.5 g of seed crystals, keeping for 2-8 hours, suction filtration,The wet product was dried at 40 C under reduced pressure to obtain tenofovir (99.28 g).Yield 91.5%The purity is 98.3%.

The synthetic route of 35180-01-9 has been constantly updated, and we look forward to future research findings.

Reference:
Patent; Zhejiang Jiuzhou Pharmaceutical Co., Ltd.; Ye Meiqi; Xu Jiankang; Wu Hao; Chen Linguo; Ye Kai; (17 pag.)CN104974188; (2019); B;,
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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 35418-07-6 as follows. Recommanded Product: Methyl 3-(4-aminophenyl)propanoate

General procedure: To a solution of 3a (1 g) in ethanol was added Pd/C (5%, 0.1 g) and the mixture was stirred for 24 hrs at room temperature in a hydrogen atmosphere under atmospheric pressure. Insoluble matters were removed using Celite, and the filtrate was concentrated in vacuo to give the desired product 4a (0.76 g) as a yellow solid. To a solution of carboxylic acid (1 equiv) in CH2Cl2 (15 mL) at 0 C was added DMAP (1 equiv) and EDCI (1 equiv). The reaction mixture was stirred at 0 C for 45 minutes. At this time 4a (1 equiv) was added and the mixture was warmed to room temperature and stirred overnight. The resulting mixture was concentrated in vacuo, partitioned between 1.0 M HCl (20 ml) and ethyl acetate (3¡Á20 mL). The combined organic layers were washed with brine (2 ¡Á 15 ml), dried over Na2SO4, filtered and concentrated in vacuo. The crude residue was purified by silica gel chromatograph using a mixture of petroleum ether/ethyl acetate (20 : 5, v/v) as eluent to afford the product as a white solid. To a solution of the obtained solid (1 equiv) in 2:3:1 THF/MeOH/H2O (18 ml) was added LiOH¡¤H2O (1.5 equiv). After stirring at room temperature for 4 h, the volatiles were removed under reduced pressure. The residue was acidified with 1N hydrochloric acid solution, and then filtered and the filter cake was washed with 5 mL of water, dried in vacuum to afford a white powder. Recrystallization from 75% EtOH gave the desired compounds 2-17 as white solid.

According to the analysis of related databases, 35418-07-6, the application of this compound in the production field has become more and more popular.

Reference:
Article; Yang, Jianyong; Li, Zheng; Li, Huilan; Liu, Chunxia; Wang, Nasi; Shi, Wei; Liao, Chen; Cai, Xingguang; Huang, Wenlong; Qian, Hai; Bioorganic and Medicinal Chemistry; vol. 25; 8; (2017); p. 2445 – 2450;,
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106-65-0, name is Dimethyl succinate, 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. Quality Control of Dimethyl succinate

EXAMPLE 26 Methyl alpha-Formylsuccinate, FIG. 1(26a) In a modification of the procedure of Fissekis and Sweet, Biochemistry 1970, 9, 3136-42, sodium methoxide (40.5 g, 0.75 mol) was suspended in dry ether (500 ml) and stirred under nitrogen at 0 C. A mixture of dimethylsuccinate (65.4 ml, 0.50 mol) and methylformate (123 ml, 2.00 mol) was added dropwise over 30 min. The reaction mixture was stirred at 0 C. for 2 hours and then at room temperature overnight. Subsequently, the reaction mixture was evaporated to a viscous brown residue which was washed once with petroleum ether and then dissolved in 3 M hydrochloric acid (160 ml). This solution was made weakly acidic with concentrated hydrochloric acid and then extracted with dichloromethane (4*250 ml). The organic phase was dried (MgSO4), filtered and evaporated under reduced pressure. The resulting residue was distilled in a kugelrohr apparatus at 60 C. and 0.6 mBar yielding 52.3 g of a mixture of the title compound and dimethyl succinate in the molar ratio 80:20 (determined by NMR) as a colorless oil. This mixture can be used directly in the following preparation. The product can be isolated free of dimethyl succinate by exchanging the extraction with dichloromethane with a continuous extraction with diethyl ether. However, in our hands this reduced the yield to 34%. Fissekis and Sweet, ibid, had reported a 62% yield. 1H-NMR (DMSO-d6/TMS): delta=3.20 (s, 2H, CH2); 3.59 (s, 3H, OMe); 3.61 (s, 3H, OMe); 7.73 (s, 1H, CHOH); 10.86 (br s, 1H, CHOH). 13C-NMR (DMSO-d6/TMS): delta=28.9 (CH2); 51.0 (OMe); 51.6 (OMe); 102.1 (C=CHOH); 156.6 (CHOH); 168.3 (COO); 171.7 (COO).

The synthetic route of 106-65-0 has been constantly updated, and we look forward to future research findings.

Reference:
Patent; ISIS Pharmaceuticals, Inc.; Perseptive Biosystems, Inc.; US6451968; (2002); B1;,
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Reference of 23786-14-3, 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. 23786-14-3, name is Methyl 4-methoxyphenylacetate belongs to esters-buliding-blocks compound, it is a common compound, a new synthetic route is introduced below.

General procedure: The methyl arylacetate (1 equiv.) and p-ABSA (1.3 equiv.) were dissolved in acetonitrile and cooled to 0 C using an ice bath under an argon atmosphere. 1,8-Diazabicycloundec-7-ene (DBU, 1.3 equiv.) was then added to the stirring mixture over the course of 5 minutes. After the addition of the DBU, the reaction mixture continued to stir at 0 C for an additional 15 minutes. Once this allotted time had passed, the ice bath was removed and the reaction mixture was stirred for 24 hours at room temperature. The resulting orange solution was quenched with saturated NH4Cl and the aqueous layer was extracted with diethyl ether (3x). The organic layer was then washed with deionized H2O to remove any residual salts. The combined organic layers were dried over MgSO4 and filtered. The organic layer was then concentrated under reduced pressure. The residue was purified via flash chromatography on silica gel (10:1 Hexanes:EtOAc).

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 4-methoxyphenylacetate, other downstream synthetic routes, hurry up and to see.

Reference:
Article; Chepiga, Kathryn M.; Qin, Changming; Alford, Joshua S.; Chennamadhavuni, Spandan; Gregg, Timothy M.; Olson, Jeremy P.; Davies, Huw M.L.; Tetrahedron; vol. 69; 27-28; (2013); p. 5765 – 5771;,
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