Tag: M.W=200-300

Application of 921222-14-2, 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. 921222-14-2 name is Ethyl 2,3-diamino-6-(methylthio)benzoate, 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 2,3-diamino-6-methylsulfanyl-benzoic acid ethyl ester (150 mg) in acetonitrile (10 mL) are added 2,3-dichlorophenyl isothiocyanate (98 muL). The reaction mixture obtained is stirred 1 hour at RT and N-(3-dimethylaminopropyl)-N’-ethylcarbodiimide hydro-chloride (EDCI, 166 mg) is added. The mixture obtained is cooled to RT, quenched with H2O and extracted with EtOAc. The organic layers obtained are combined, dried over MgSO4, filtrated and solvent is evaporated to afford the title compound (LC/MS Rt=3.55, [M]+=395.93 and 397.89 and 399.89).

At the same time, in my other blogs, there are other synthetic methods of this type of compound, Ethyl 2,3-diamino-6-(methylthio)benzoate, and friends who are interested can also refer to it.

Reference:
Patent; NOVARTIS AG; NOVARTIS PHARMA GMBH; WO2007/9774; (2007); A1;,
Ester – Wikipedia,
Ester – an overview | ScienceDirect Topics

Application of 52727-57-8, These common heterocyclic compound, 52727-57-8, name is Methyl 2-amino-5-bromobenzoate, 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.

Example 88:Methyl 2-amino-5-[4-(methylsulfonyImethyl)-6-morpholin-4-yl-pyrimidin-2- yljbenzoateA mixture of methyl-2-amino-5-bromobenzoate (250 mg), potassium acetate (320 mg) and bis(pinacolato)diboron (332 mg) in 1,4-dioxane (10 mL) was degassed for 5 minutes. 1,1′- Bis(diphenylphosphino)ferrocenedichloropalladium(II) dichloromethane adduct (54 mg) was added and the reaction was heated to 8O0C for 2.5 hours. 2-Chloro-4-(methylsulfonylmethyl)-6-mophiholin-4-yl-pyrimidine (381 mg), ethanol (0.75 mL), a 2M solution of sodium carbonate (2.7 mL) and additional 1,1′- bis(diphenylphosphino)ferrocenedichloropalladium(II) dichloromethane adduct (54 mg) were added and the heating was continued for a further 3.5 hours. The cooled reaction mixture was loaded on a SCX-2 (10 g), removed with 7N ammonia in methanol and the solution concentrated in vacuo. The residue was chromatographed on silica, eluting with 50% ethyl acetate in DCM, to give the desired material as a yellow solid (82 mg). Mass Spectrum; MH+ 407 NMR Spectrum: 1H NMR (DMSO-d6) 53.22 (3H, s), 3.69 (4H, s), 3.73 (4H, s), 3.84 (3H, s), 4.49 (2H, s), 6.77 (IH, s), 6.87 (IH, d), 7.05 (2H, s), 8.24 (IH, d), 8.79 (IH, s)

The synthetic route of 52727-57-8 has been constantly updated, and we look forward to future research findings.

Reference:
Patent; ASTRAZENECA AB; ASTRAZENECA UK LIMITED; WO2007/80382; (2007); A1;,
Ester – Wikipedia,
Ester – an overview | ScienceDirect Topics

Application of 1000342-11-9, A common heterocyclic compound, 1000342-11-9, name is Methyl 3-amino-5-bromo-2-methylbenzoate, molecular formula is C9H10BrNO2, 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.

Methyl 5-bromo-2-methyl-3-((tetrahydro-2H-pyran-4-yl) amino) benzoate (2) A reactor was charged with methyl 3-amino-5-bromo-2-methylbenzoate (455.8 g, 1.87 mol), 1,2- Dichloroethane (4.56 L), and acetic acid (535 ml, 9.34 mol). To the mixture were added dihydro-2H-pyran-4(3H)-one (280 g, 2.80 mol) and sodium triacetoxyborohydride (594 g, 2.80 mol) maintaining the internal temperature below 40 C. The mixture was stirred at 25 C for 2.5 h and then the reaction was quenched with a solution of sodium hydroxide (448 g, 11.20 mol) in water (5.61 L). After stirring for 20 minutes at ambient temperature, the organic layer was separated and the aqueous layer was extracted with ethyl acetate (3.65 L). The organic layers were combined, washed with brine (1.5 L), and concentrated under vacuum. The residue was treated with ethyl acetate (1.8 L) and heated to 65-70 C. The mixture was stirred at 65-70 C for 15 minutes to give a clear solution and then treated with n-heptane (7.3 L) maintaining the temperature between 60-70 C. Once the heptane was completely added to the solution, the mixture was held at 65-70 C for 15 minutes and then allowed to cool to 18- 22 C over 3 h. The resulting suspension was stirred at 18-22 C for 4 h, cooled to 0-5 C over 1 h, and held at 0-5 C for 2 h. The precipitate was filtered, washed twice with n-heptane (1.4 L), and dried under vacuum to give the title compound (540 g, 88%). The XRPD pattern of this compound is shown in Figure 17.

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; EPIZYME, INC.; EISAI R&D MANAGEMENT CO.LTD.; KUNTZ, Kevin, Wayne; HUANG, Kuan-chun; CHOI, Hyeong, Wook; SANDERS, Kristen; MATHIEU, Steven; CHANDA, Arani; FANG, Frank; WO2013/155317; (2013); A1;,
Ester – Wikipedia,
Ester – an overview | ScienceDirect Topics

Some common heterocyclic compound, 618-89-3, name is Methyl 3-bromobenzoate, molecular formula is C8H7BrO2, 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. Computed Properties of C8H7BrO2

In a 25 mL round-bottomed flask, toluene (10 mL) was degassed with argon for 20 min. Under a flow of argon, Pd(OAc)2 (0.05 g, 0.23 mmol), BINAP (0.23 g, 0.37 mmol) and Cs2CO3 (2.12 mmol, 6.51 mmol) were added and left to stir for a further 20 min. To the mixture, methyl (3-bromobenzoate) 1 (1.01 g, 4.65 mmol) and aniline 2 (0.51 mL, 5.58 mmol) were added. The reaction was stirred at 120 C and monitored by thin layer chromatography (TLC) for 24 h. Upon completion, the reaction was cooled to room temperature and filtered through Celite, with hexane as the eluent, followed by concentration under reduced pressure. The residue was purified by flash column chromatography on silica eluting with hexane/ethyl acetate (90:10) (Rf 0.23) to afford 0.87 g (82%) of 3 as a pale yellow solid; M.p. 110-112 C (literature M.p. 110-111 C) [40]; 1H NMR (400 MHz/CDCl3)/ppm, delta = 3.90 (s, 3H,-COOCH3), 5.81 (s, 1H, -NH), 6.98 (app. t, 1H, app J = 8 Hz, CHparaC4H4-NH), 7.09 (app. d, 2H, CHparaC2H2metaC2H2ortho-NH), 7.23 (m, 1H, HN-CH-C(COOCH3)-CHCHCH-), 7.29 (m, 3H, C2H2ortho-HN-CH-C(COOCH3)-CHCHCH-), 7.57 (app. d, 1H, HN-CH-C(COOCH3)-CH), 7.72 (m, 1H, HN-CHC(COOCH3)); 13C NMR (100 MHz/CDCl3)/ppm, delta = 52.2, 118.2, 118.4, 121.5, 121.77, 121.80, 129.4, 129.3, 131.4, 142.4, 143.6, 167.1; Found [M+H]+ (C14H14NO2) m/z 228.1019 (Calc. 228.1025); IR (ATR) v/cm-1: 3358, 3030, 1694, 1578, 1294, 744.

These compound has a wide range of applications. It is believed that with the continuous development of the source of the synthetic route 618-89-3, its application will become more common.

Reference:
Article; Higgins, Clare L.; Filip, Sorin V.; Afsar, Ashfaq; Hayes, Wayne; Tetrahedron; vol. 75; 51; (2019);,
Ester – Wikipedia,
Ester – an overview | ScienceDirect Topics

Some common heterocyclic compound, 136333-97-6, name is Methyl 4-(2-bromoethyl)benzoate, molecular formula is C10H11BrO2, 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. Quality Control of Methyl 4-(2-bromoethyl)benzoate

8e) 4-(2-Bromoethyl)benzyl alcohol To a suspension of LiAIH4 (4.5 mmol; 0.172 g) in anhydrous THF(5.0 ml) cooled to 00C was added dropwise a solution of methyl 4-(2- bromoethyl)benzenecarboxylate (1.0 g; 4.1 mmol) in anhydrous THF(10.0 ml). The reaction mixture was stirred for 5 minutes at room temperature and, after adding ice, was filtered through a Bchner filter.The solvent was removed under reduced pressure and the residue was extracted with ethyl acetate (3 * 100 ml). The combined organic phases were washed with saturated NaCI solution, dried over sodium sulfate and evaporated under reduced pressure. 800 mg (82.6%) of pure product were thus obtained as an oil .1H NMR (CDCI3, delta ppm): 3.22 (t, 2H); 3.62 (t, 2H); 4.72 (s, 2H); 7.25- 7.39 (m, 4H).

These compound has a wide range of applications. It is believed that with the continuous development of the source of the synthetic route 136333-97-6, its application will become more common.

Reference:
Patent; AZIENDE CHIMICHE RIUNITE ANGELINI FRANCESCO A.C.R.A.F. S.p.A.; ALISI, Maria Alessandra; CAZZOLLA, Nicola; COSTI, Roberta; DI SANTO, Roberto; FURLOTTI, Guido; GUGLIELMOTTI, Angelo; POLENZANI, Lorenzo; WO2010/12611; (2010); A1;,
Ester – Wikipedia,
Ester – an overview | ScienceDirect Topics

Some common heterocyclic compound, 2557-13-3, name is Methyl 3-(trifluoromethyl)benzoate, molecular formula is C9H7F3O2, 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. Application In Synthesis of Methyl 3-(trifluoromethyl)benzoate

EXAMPLES 24 AND 25(3-(3-(Trifluoromethyl)phenyl)-4,5-dihydronaphtho[l,2-c]isoxazol-7-yl)methanol (24) andl-((3-(3-(Trifluoromethyl)phenyl)-4,5-dihydronaphtho[l,2-c]isoxazol-7- -3-carboxylic acid (25)[00331] To 6-vinyl-3,4-dihydronaphthalen-l(2H)-one oxime (Intermediate 1, 0.151 g, 0.808 mmol) was added 5 mL of toluene and the contents were concentrated under reduced pressure. The resulting solid was kept under high vacuum for 10 min. The white solid was cooled to 0 C and lithium diisopropylamide (2.0 M, 0.8 mL, 1.61 mmol) was added drop wise over a period of 3 min. The reaction mixture was stirred at 0 C for 20 min., then methyl 3-(trifluoromethyl)benzoate (0.087 mL, 0.539 mmol) was added dropwise over a period of 1 min. at 0 C. After 10 min. at 0C, concentrated sulfuric acid (0.2 mL) was added dropwise at 0 C and the reaction was stirred for 20 minutes. Water (2 mL) was added and the homogenous solution was heated at 60 C for ~2 hr. The reaction mixture was stirred overnight at room temperature. The contents were concentrated under reduced pressure. Next, 5 mL of dioxane was added and the contents were heated at 100 C for 1.5 hr. The reaction mixture was concentrated under reduced pressure and partitioned between ethyl acetate (20 mL) and sat. aq. sodium bicarbonate (10 mL). The ethyl acetate layer was dried over sodium sulfate, concentrated under reduced pressure, and purified by silica gel column chromatography (hexane/ethyl acetate). Fractions corresponding to the product were collected and concentrated to yield 3-(3-(trifluoromethyl)phenyl)-7-vinyl-4,5-dihydronaphtho[l,2-c]isoxazole (0.15 g, 0.439 mmol, 82 % yield) as a pale yellow solid. LC/MS M+1 = 342.

These compound has a wide range of applications. It is believed that with the continuous development of the source of the synthetic route 2557-13-3, its application will become more common.

Reference:
Patent; BRISTOL-MYERS SQUIBB COMPANY; DHAR, T.G. Murali; XIAO, Hai-Yun; WATTERSON, Scott Hunter; KO, Soo S.; DYCKMAN, Alaric J.; LANGEVINE, Charles M.; DAS, Jagabandhu; CHERNEY, Robert J.; WO2011/59784; (2011); A1;,
Ester – Wikipedia,
Ester – an overview | ScienceDirect Topics

Reference of 676621-95-7,Some common heterocyclic compound, 676621-95-7, name is Ethyl 3-(4-fluorophenyl)-2,2-dimethylpropanoate, molecular formula is C13H17FO2, 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.

Preparation of3- (4-fluorophenyl)-2, 2- dimethylpropionic acid A mixture of 3- (4-fluorophenyl)-2, 2-dimethylpropionic acid ethyl ester (10.0 g, 44.6 mmol, see Part 1 of Example 25a) and a solution of sodium hydroxide (25 g) in water (110 mL) was heated at refluxfor 18 h and cooled to room temperature. The solution was stirred on an ice bath and acidified with, concentrated aqueous hydrochloric acid. The resulting precipitate was collected by filtration, washed with water and dried under vacuum. The residue was stirred with dichloromethane and filtered, and the filtrate was concentrated to provide an off-white solid (7.60 g, 87%). OH NMR (300 mHz, CDC13) 6 7.14 (m, 2H), 6.98 (t, J = 9 Hz, 2H), 2.88 (s, 2H), 1.22 (s, 6H); mass spec (ES-) m/z 195.2 (100%,M-H+).

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-(4-fluorophenyl)-2,2-dimethylpropanoate, its application will become more common.

Reference:
Patent; BRISTOL-MYERS SQUIBB COMPANY; WO2005/48932; (2005); A2;,
Ester – Wikipedia,
Ester – an overview | ScienceDirect Topics

Related Products of 541-16-2, A common heterocyclic compound, 541-16-2, name is Di-tert-Butyl malonate, molecular formula is C11H20O4, 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.

Step 1: Preparation of 2-ethylcyclopropane-1,1-dicarboxylic acid di-tert-butyl ester, shown below To a suspension of benzyltriethylammonium chloride (21.0 g, 92.2 mmol) in a 50% aqueous NaOH solution (92.4 g in 185 mL H2O) was added 1,2-dibromobutane (30.0 g, 138.9 mmol) and di-tert-butylmalonate (20.0 g, 92.5 mmol). The reaction mixture was vigorously stirred for 18 hours at room temperature and treated with a mixture of ice and water. The crude product was extracted with dichloromethane (3*) and sequentially washed with water (3*), and brine. The organic extracts were combined, dried (MgSO4), filtered, and concentrated in vacuo. The resulting residue was purified by flash column chromatography (100g SiO2, 3% diethyl ether in hexane) to provide the desired product (18.3 g, 67.8 mmol, 73% yield) which was used directly in the next reaction.

The synthetic route of 541-16-2 has been constantly updated, and we look forward to future research findings.

Reference:
Patent; Bristol-Myers Squibb Company; US2009/304626; (2009); A1;,
Ester – Wikipedia,
Ester – an overview | ScienceDirect Topics

Adding a certain compound to certain chemical reactions, such as: 154825-97-5, name is Methyl 2-(4-bromophenyl)-2,2-dimethylacetate, 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 154825-97-5, COA of Formula: C11H13BrO2

To a suspension of lithium aluminum hydride (2.95 g, 78 mmol, 2 equiv.) in THF (70 mL) at 0C was added a solution of methyl 2-(4-bromophenyl)-2-methylpropanoate (10 g, 39 mmol, 1 equiv.) in THF (60 mL) dropwise. After stirring at 0C for 1 h, the reaction was quenched sequentially with 3 mL of water, 9 mL of a 5% sodium hydroxide solution and 3 mL of water. It was filtered on a Celite pad using ether as an eluent. The solvent was evaporated and the residue was purified by bulb-to-bulb distillation (2-4 mbar, l30C) to afford 2-(4-bromophenyl)-2-methylpropan-l-ol (8.27 g, 93% yield).1H NMR: 1.30 (s, 6H), 3.57 (s, 2H), 7.25 (d, J = 8.6 Hz, 2H), 7.45 (d, J = 8.6 Hz, 2H).13C NMR: 145.6 (s), 131.4 (d, 2C), 128.2 (d, 2C), 120.1 (s), 72.8 (t), 39.9 (s), 25.2 (q,2C).

At the same time, in my other blogs, there are other synthetic methods of this type of compound, Methyl 2-(4-bromophenyl)-2,2-dimethylacetate, and friends who are interested can also refer to it.

Reference:
Patent; FIRMENICH SA; COULOMB, Julien; ODDON, Gilles; (33 pag.)WO2019/141761; (2019); A1;,
Ester – Wikipedia,
Ester – an overview | ScienceDirect Topics

Electric Literature of 154825-97-5, 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. 154825-97-5, name is Methyl 2-(4-bromophenyl)-2,2-dimethylacetate belongs to esters-buliding-blocks compound, it is a common compound, a new synthetic route is introduced below.

Step A: Preparation of 2-(4-Bromophenyl)-2-methylpropanoic acid; [0525] A solution of methyl 2-(4-bromophenyl)-2,2-dimethylacetate(3880 muL, 15090 mumol) in EtOH (80 mL) and water (20 mL) was treated with KOH (4233 mg, 75450 mumol). The reaction was heated to 900C. After 15 hours, the reaction was cooled to 23C and concentrated in vacuo. The crude mixture was partitioned between water/diethyl ether (150 mL each). The aqueous layer was separated and extracted with diethyl ether (100 mL). The combined ether layers were then extracted with a IN NaOH solution (25 mL). The combined aqueous washes were acidified with concentrated HCl to pH = 2.0 and extracted with EtOAc (3 x 100 mL). The combined EtOAc layers were dried over MgSO4, and concentrated in vacuo to afford 3144 mg of 2-(4- bromophenyl)-2-methylpropanoic acid.

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 2-(4-bromophenyl)-2,2-dimethylacetate, other downstream synthetic routes, hurry up and to see.

Reference:
Patent; AMGEN INC.; WO2008/76427; (2008); A2;,
Ester – Wikipedia,
Ester – an overview | ScienceDirect Topics