Month: March 2021

Application of 134-20-3, These common heterocyclic compound, 134-20-3, name is Methyl 2-aminobenzoate, 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 round bottom flask was added CuBr2 (33 mmol, 7.40 g), EtOH (250 mL) and 14a (66 mmol, 10.00 g). The mixture was stirred at 35C for 2 h. Then, another portion of CuBr2 (33 mmol, 7.40 g) was added, and the mixture was continuously stirred for 1 h at 35C before being heated at reflux. After the completion of the reaction, the mixture was cooled to room temperature, and the solvent was removed under reduced pressure. To the residue was added ammonia hydroxide (170 mL, 25% w/v) with vigorous stirring. After being stirred for 3 h at room temperature, the mixture was filtered and washed with ammonia hydroxide (5 mL ¡Á3) and water (20 mL ¡Á5). The filter cake was recrystallized with MeOH (25 mL) to produce 14bb in 95% yield as white solid. Methyl 2-amino-3,5-dibromobenzoate (14bb) White solid, mp 89.9-91.6 C, 95% yield. 1H NMR (CDCl3) delta 8.00 (d, J = 2.1 Hz, 1H), 7.71 (d, J = 2.1 Hz, 1H), 6.38 (s, 2H), 3.91 (s, 3H). 13C NMR (CDCl3) delta 167.0, 146.6, 139.1, 133.1, 112.6, 111.1, 106.5, 52.2. MS (ESI): m/z calcd for C8H8Br2NO2: 307.9 [M+H]+; found: 308.1 (79Br, 79Br, 30%), 310.1 (79Br, 81Br 100%), 312.1 (81Br, 81Br 30%).

Statistics shows that Methyl 2-aminobenzoate is playing an increasingly important role. we look forward to future research findings about 134-20-3.

Reference:
Article; Zhao, Hong-Yi; Yang, Xue-Yan; Lei, Hao; Xin, Minhang; Zhang, San-Qi; Synthetic Communications; vol. 49; 11; (2019); p. 1406 – 1415;,
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Synthetic Route of 10602-06-9, A common heterocyclic compound, 10602-06-9, name is Methyl 3-ethynylbenzoate, molecular formula is C10H8O2, 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.

A. Under the conditions of example 5A, 9.2 g of 3-(3-hydroxy-6-iodo-2-pyridyl)-propionic acid methyl ester is reacted with 4.8 g of 3-ethinylbenzoic acid methyl ester, worked up, and the crude product is chromatographed on silica gel with hexane/0-20% ethyl acetate. 4.7 g of 3-{3-hydroxy-6-[2-(3-methoxycarbonylphenyl)-ethinyl]-2-pyridyl}-propionic acid methyl ester of melting point 125-127 C. is obtained. IR(CHCl3): 3250 (broad), 2950, 1718, 1453, 1435, 1258, 1098, 1010 cm-1.

The synthetic route of 10602-06-9 has been constantly updated, and we look forward to future research findings.

Reference:
Patent; Schering Aktiengesellschaft; US5624943; (1997); A;,
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Synthetic Route of 609-12-1, A common heterocyclic compound, 609-12-1, name is Ethyl 2-bromo-3-methylbutanoate, molecular formula is C7H13BrO2, 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: General Method 4C: N-Alkylation of 2-pyridinonederivatives with the appropriate 2-bromo-or 2-chloropropanoic ester derivativesin the presence of sodium hydride/lithium bromide Under argon and at 0 C, 1.25eq. of sodium hydride (60% in mineral oil) were added to a solution of 1.0 eq.of the appropriate 2-pyridinone derivative in dimethylformamide (5-10 ml/mmol),and the mixture was stirred at 0 C for 10-20 min. 2.0 eq. of lithium bromidewere then added, the reaction mixture was stirred at RT for 15 min, 1.25 eq. ofthe appropriate 2-bromo- or 2-chloropropanoic ester derivative were added andthe mixture was stirred at 65 C. After removal of the DMF and addition ofwater/ethyl acetate and phase separation, the organic phase was washed withwater, dried (sodium sulphate), filtered and concentrated under reducedpressure. The crude product was then purified either by flash chromatography(silica gel 60, mobile phase: cyclohexane/ethyl acetate mixtures or dichloromethane/methanol mixtures) or bypreparative HPLC (Reprosil C18, water/acetonitrile gradient or water/methanolgradient).500 mg (2.9 mmol) of 4-bromopyridin-2(1H)-one and 841mg (4.02 mmol) of ethyl 2-bromo-3-methylbutanoate (racemate) in the presence of1.15 eq. of sodium hydride and 2.3 eq. of lithium bromide were reactedaccording to General Method 4C. Yield: 260 mg (purity92%, 28% of theory)

The synthetic route of 609-12-1 has been constantly updated, and we look forward to future research findings.

Reference:
Patent; Bayer Pharma Aktiengesellschaft; Rurik, Jujane; Hilliswe, Alexander; Strassburke, Yulia; Hidemeyer, Stefan; Smith, Martina Victoria; Schlemmer, Karl-Heinz; Terstigen, Adrian; Buchmuller, Anya; Gerdes, Hirstoph; Schappe, Martina; Kinchel, Tom; Teller, Henryk; Shirok, Hartmut; Klar, Juergen; Jimenez, Nunez Eloisa; (352 pag.)KR2015/137095; (2015); A;,
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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. 2475-80-1, name is Methyl 2-amino-5-methoxybenzoate, A new synthetic method of this compound is introduced below., SDS of cas: 2475-80-1

Example 27 Synthesis scheme for the compound of formula IA2 A mixture of 6,6-dimethyl-8-oxo-3,4,5,6,7,8-hexahydro-2H-benzo[0][ l ,4]thiazine-3- carboxylate (0.54 g, 1.0 equiv) and 3 drops of DMF in dichloromethane ( l OmL) was cooled at – 10~0C. Oxalyl chloride (0.51 g, 2.0 equiv) was added dropwise into the mixture at – 10~0C, the mixture was kept at -10~0C for another 1 hour with stirring. The solution was concentrated under reduced pressure to give (R)-ethyl 8-chloro-6,6-dimethyl-3,5,6,7-tetrahydro-2H- benzo[¡ê][l ,4]thiazine-3-carboxylate as yellow oil. The residue was diluted with ethanol (1 1 niL, 20 vol), methyl 2-amino-5-methoxybenzoate (0.72 g, 2.0 equiv) was added into the (R)-ethyl 8- chloro-6,6-dimethyl-3,5,6,7-tetrahydro-2H-benzo[Z)][ l ,4]thiazine-3-carboxyIate solution, the resulting mixture was kept at 20~30C for 20 hour with stirring. The solution was concentrated under reduced pressure. The residue was purified by column chromatography (mobile phase: DCM/MeOH = 100/1-20/1) to give (¡ê)-methyl 2-((3-((2-ethoxy-2-oxoethyl)amino)-5,5- dimethylcyclohex-2-en-l -ylidene)amino)-5-methoxybenzoate.

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; ELKIMIA; ABOU-KHALIL, Elie; RAEPPEL, Stephane; RAEPPEL, Franck; WO2013/181741; (2013); A1;,
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Application of 42122-75-8,Some common heterocyclic compound, 42122-75-8, name is Methyl 5-amino-2-chlorobenzoate, molecular formula is C8H8ClNO2, 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.

1.1 2-Chloro-5-phenylamino-benzoic acid methyl ester Cs2CO3 (2.79 g), palladium(II) acetate (82 mg), 2,2′-bis(diphenylphosphino)-1,1′-binaphthalene (228 mg), iodobenzene (0.69 mL) and methyl-5-amino-2-chlorobenzoate (1.13 g) were placed in a flask and flushed with argon. Dioxane (18 mL) was added and the reaction mixture was heated to 100 C. for 24 h. After cooling to RT, it was diluted with Et2O, filtered over a pad of celite and the filtrate was concentrated in vacuo. The crude material was purified by CC (Hept/EtOAc 1/0 to 8/2) to give 1.18 g of the titled compound as a light yellow solid. LC-MS (A): tR=1.05 min; [M+H]+: 262.55.

The synthetic route of 42122-75-8 has been constantly updated, and we look forward to future research findings.

Reference:
Patent; Actelion Pharmaceuticals Ltd.; Hilpert, Kurt; Hubler, Francis; Murphy, Mark; Renneberg, Dorte; US2014/73651; (2014); A1;,
Ester – Wikipedia,
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Electric Literature of 6091-64-1, 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. 6091-64-1, name is Ethyl 2-bromobenzoate, This compound has unique chemical properties. The synthetic route is as follows.

Example 4 To a solution (25 ml) of 2-(4-trifluoromethylphenyl)furan (3.18 g) in tetrahydrofuran was added dropwise n-butyl lithium (1.6 M solution in hexane, 10.0 ml) under an argon atmosphere at -78C. This mixed solution was heated to room temperature, and a solution (30 ml) of zinc chloride (2.25 g) in tetrahydrofuran was added. This mixture was stirred for 1 hr., and then ethyl 2-bromobenzoate (2.38 ml) and tetrakis (triphenylphosphine)palladium (0.433 g) were added. This mixture was stirred overnight under an argon atmosphere, and then poured into 0.5 M hydrochloric acid. The mixture was extracted with ethyl acetate. The organic layer was washed with saturated aqueous sodium hydrogen carbonate solution and saturated brine, dried over anhydrous magnesium sulfate and concentrated. The residue was purified by silica gel column chromatography (hexane:ethyl acetate=10:1, volume ratio) to give ethyl 2-[5-(4-trifluoromethylphenyl)-2-furyl]benzoate (2.54 g, yield 47%) as a pale-yellow oil. NMR (CDCl3) delta: 1.12 (3H, t, J = 7.2 Hz), 4.27 (2H, q, J = 7.2 Hz), 6.70 (1H, d, J = 3.6 Hz), 6.87 (1H, d, J = 3.6 Hz), 7.41 (1H, dt, J = 1.4, 7.4 Hz), 7.53 (1H, dt, J = 1.4, 7.4 Hz), 7.61-7.79 (6H, m).

The chemical industry reduces the impact on the environment during synthesis Ethyl 2-bromobenzoate. I believe this compound will play a more active role in future production and life.

Reference:
Patent; Takeda Chemical Industries, Ltd.; EP1405636; (2004); A1;,
Ester – Wikipedia,
Ester – an overview | ScienceDirect Topics

These common heterocyclic compound, 99548-55-7, name is Methyl 4-bromo-2-methylbenzoate, 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. SDS of cas: 99548-55-7

Example 17: 4-cyano-2-methylbenzoic acid methyl ester; To a solution of 4-bromo-2-methylbenzoic acid (108 g, 471 mmol) inLambda/,Lambda/-dimethylformamide (4 L) under a nitrogen atmosphere was added zinc (II) cyanide (88.5 g, 753.6 mmol) and tetrakis(triphenylphosphine)palladium (65 g, 56.60 mmol). The reaction mixture was stirred at 1000C for 16 hours. The reaction mixture was diluted with toluene and the phases were separated. The aqueous phase was extracted twice with toluene. The combined organic phases were washed with brine and saturated aqueous ammonium hydroxide, dried over sodium sulfate and concentrated. The residue was purified by column chromatography on silica gel (eluent: ethyl acetate / cyclohexane 1 :5) to give 4-cyano-2- methylbenzoic acid methyl ester (73 g, 89percent yield). 1H NMR (400 MHz, CDCl3): 7.78 (d, IH), 7.52 (m, 2H), 3.92 (s, 3H), 2.62 (s, 3H) ppm.

The synthetic route of Methyl 4-bromo-2-methylbenzoate has been constantly updated, and we look forward to future research findings.

Reference:
Patent; SYNGENTA PARTICIPATIONS AG; MAIENFISCH, Peter; GODFREY, Christopher Richard Ayles; JUNG, Pierre Joseph Marcel; HUETER, Ottmar Franz; RENOLD, Peter; WO2010/127928; (2010); A1;,
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Adding a certain compound to certain chemical reactions, such as: 1000342-11-9, name is Methyl 3-amino-5-bromo-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 1000342-11-9, category: esters-buliding-blocks

01629] Step 4: Synthesis of methyl 5-bromo-2-methyl-3-[(oxan-4-yl)amino]benzoate[01630] To a solution of methyl 3-amino-5-bromo-2-methylbenzoate (3.0 g, 12 mmol) in 1 ,2- dichloroethane (48 ml) under nitrogen, was added oxan-4-one (2.3 ml, 25 mmol) followed by acetic acid (4.2 ml, 74 mmol). The reaction mixture was stirred for 5 minutes before the addition of sodium triacetoxyborohydride (7.8 g, 37 mmol). After stirring for 64 hours, deionized water (100 ml) was added and the mixture was neutralized with solid NaHC03. The phases were separated and the aqueous layer was extracted with EtOAc (4 x 50 ml). The combined organic extracts were dried over MgS04, filtered and concentrated in-vacuo. The residue was purified by flash column chromatography (50g silica, Isolute cartridge, 10-30% EtOAc:Heptanes) to give the title compound (3.5 g 85%) as a white solid. LC-MS 99.8m/z= 327.9, 328.9, 329.9, 330.9; NMR (500 MHz, Chloroform-d) delta ppm 7.24 (d, J=1.73 Hz, 1 H) 6.85 (d, J=l .58 Hz, 1 H) 4.03 (dt, J=l 1 .82, 3.3 1 Hz, 2 H) 3.88 (s, 3 H) 3.66 (br.s., 1 H) 3.56 (td, J=U .55, 1 .97 Hz, 2 H) 3.47 – 3.55 (m, 1 H) 2.24 (s, 3 H) 2.06 (d, J= 13.56 Hz, 2 H) 1.47 – 1 .60 (m, 2 H).

At the same time, in my other blogs, there are other synthetic methods of this type of compound, Methyl 3-amino-5-bromo-2-methylbenzoate, and friends who are interested can also refer to it.

Reference:
Patent; EPIZYME, INC.; EISAI CO., LTD.; KUNTZ, Kevin, Wayne; CHESWORTH, Richard; DUNCAN, Kenneth, William; KEILHACK, Heike; WARHOLIC, Natalie; KLAUS, Christine; ZHENG, Wanjun; WO2012/142513; (2012); A1;,
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Electric Literature of 43088-72-8,Some common heterocyclic compound, 43088-72-8, name is 6-Methoxyisochroman-3-one, molecular formula is C10H10O3, 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 6-methoxyisochroman-3-one 3242 (300 mg, 1.68 mmol), amine analogues (a – g) (2.52 mmol) and AlCl3 (45.0 mg, 0.340 mmol) were combined under anhydrous conditions in a sealed tube and heated at 150 oC for 48 h. The reaction mixture was poured into aqueous 1 N HCl (5.0 mL) and extracted with EtOAc (20 mL x 2) to afford a brown residue which was purified with column chromatography (30:70 EtOAc/Hexane). 6-Methoxy-2-(4?-methylthiazol-2-yl)-1,2-dihydroisoquinolin-3(4H)-one (33a) was obtained from 32 as a pale yellow residue (162 mg, 35%), Rf 0.76 (50:50 EtOAc/Hexane). 1H NMR (300 MHz, CDCl3): deltaH 7.27-7.25 (m, 1H, ArH), 6.84-6.75 (m, 2H, ArH), 6.58 (s, 1H, thiazole-H), 5.29 (s, 2H, ArCH2N), 3.83-3.80 (m, 5H, overlapping signals-OMe and CH2), 2.33 (s, 3H, thiazole-Me). 13C NMR (75 MHz, CDCl3): deltaC 17.7 (thiazole-Me), 39.1 (ArCH2), 49.7 (ArCH2N), 55.7 (OMe), 110.0 (thiazole-CH), 112.5 (ArCH), 113.3 (ArCH), 123.7(ArCH), 127.4 (ArC), 132.8 (ArC), 147.0 (thiazole-CMe), 158.7 (thiazole-ArCN), 159.8 (C-O), 168.4 (C=O). HRMS ESI+ calcd for C14H15N2O2S [M+H]+, 275.0854, found, 275.0855.

These compound has a wide range of applications. It is believed that with the continuous development of the source of the synthetic route 6-Methoxyisochroman-3-one, its application will become more common.

Reference:
Article; Mabank, Tanya; Alexandre, Kabamba B.; Pelly, Stephen C.; Green, Ivan R.; van Otterlo, Willem A.L.; Arkivoc; vol. 2019; 4; (2019);,
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Related Products of 110661-91-1,Some common heterocyclic compound, 110661-91-1, name is tert-Butyl 4-bromobutanoate, molecular formula is C8H15BrO2, 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.

Part A Preparation of 6-[(5-Hydroxypentyl)oxy]-2-(4-t-butoxy-4-oxobutyloxy)benzenepropanoic Acid Methyl Ester A mixture of 2-hydroxy-6-[(5-hydroxypentyl)oxy]-benzenepropanoic acid methyl ester (2.04 g, 7.23 mmol) (as described by Cohen, N. EP Appl. 531,823), t-butyl 4-bromobutyrate (1.93 g, 8.67 mmol), and K2CO3 (2.29 g, 16.6 mmol) in DMSO (60 mL) was stirred at ambient temperatures under nitrogen for 21 h. The solids were removed by filtration and the filtrate was diluted with water (100 mL), and extracted with EtOAc (3*100 mL). The combined organic extracts were washed with water and sat. NaCl, dried (MgSO4), and concentrated to give product as a yellow oil (2.98 g). A portion (487 mg) was purified by silica gel flash chromatography (40:60 EtOAc/hexanes) to give the title compound as a colorless oil (367 mg, 73.3%). 1H NMR (CDCl3): 7.08 (t, J=8.2 Hz, 1H), 6.48 (d, J=8.2 Hz, 2H), 4.00-3.89 (m, 4H), 3.70-3.62 (m, 5H), 3.04-2.93 (m, 2H), 2.50-2.39 (m, 4H), 2.11-1.99 (m, 2H), 1.88-1.75 (m, 2H), 1.72-1.52 (m, 5H), 1.43 (s, 9H); MS: m/e 447.3 [M+Na].

These compound has a wide range of applications. It is believed that with the continuous development of the source of the synthetic route tert-Butyl 4-bromobutanoate, its application will become more common.

Reference:
Patent; Bristol-Myers Squibb Pharma Company; US6416733; (2002); B1;; ; Patent; Carpenter JR., Alan P.; US2003/3049; (2003); A1;; ; Patent; Barrett, John Andrew; Cheesman, Edward Hollister; Harris, Thomas David; Liu, Shuang; Rajopadhye, Milind; Sworin, Michael; US2003/124053; (2003); A1;,
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