Category: esters-buliding-blocks

Electric Literature of 42726-73-8,Some common heterocyclic compound, 42726-73-8, name is tert-Butyl methyl malonate, molecular formula is C8H14O4, 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 t-butyl methyl malonate (0.69 g, 3.9 mmol) in dimethylformamide (10 mL) was treated with sodium hydride (60percent in mineral oil, 0.16 g, 3.9 mmol) at 60° C. for 30 minutes. After cooling to room temperature, a solution of the compound of Example 1(a) (1.2 g, 3.0 mmol) in dimethylformamide (10 mL) was added dropwise. After stirring at room temperature overnight, the reaction mixture was diluted with ethyl acetate/hexanes (1:1, 100 mL) and washed with water (5.x.50 mL) and brine (50 mL), and dried (Na2SO4). After removing the solvent under the reduced pressure, the residue was dissolved in toluene (100 mL) and p-toluenesulfonic acid monohydrate (0.2 g, 1.0 mmol) was added. The resulting mixture was heated to reflux for 2h. After cooling to room temperature, the mixture was diluted with ethyl acetate (50 mL), washed with saturated NaHCO3 (50 mL) and brine (50 mL), and dried (Na2So4). After removing the solvent under the reduced pressure, the residue was purified by flash column chromatography (silica gel, 1:4 EtOAc/hexanes) to afford 0.47 g (40percent) of the title compound as a brown oil: 1H NMR (CDCl3) delta 7.34 (m, 5H), 4.55 (s, 2H), 3.67 (s, 3H), 3.54 (m, 3H), 3.33 (m, 2H), 3.05 (m, 1H), 2.68 (m, 3H), 2.16 (m, 1H), 1.25-1.70 (m, 12H), 0.93 (t, 3H). MS(ES) m/e 390 [M+H]+.

The synthetic route of 42726-73-8 has been constantly updated, and we look forward to future research findings.

Reference:
Patent; Xiang, Jia-Ning; Christensen IV, Siegfried B.; Liao, Xiangmin; Cummings, Maxwell D.; US2004/77856; (2004); 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. 37746-78-4, name is (E)-Ethyl 4-bromobut-2-enoate, This compound has unique chemical properties. The synthetic route is as follows., Safety of (E)-Ethyl 4-bromobut-2-enoate

Intermediate 26 Ethyl (2E)-4-(5-bromo-2-nitrophenoxy)but-2-enoate 5-Bromo-2-nitrophenol (10 g, 45.9 mmol) and K2CO3 (8.24 g, 59.6 mmol) were suspended in NMP (81 mL) (a bright red suspension) and ethyl 4-bromocrotonate (10.26 mL, 59.63 mmol) was added dropwise at room temperature. The reaction was stirred at room temperature over night (20 h). The mixture was poured into ice/water (500 mL) and stirred for 30 min. The precipitate was collected by filtration and washed with water (2*200 mL), air dried for 10 min and then washed with heptane (200 mL). Heptane (200 mL) was added to the solid and stirred for 1 h. The solid was filtered off, washed with heptane (2*50 mL) and dried in vacuo to afford a beige solid. The title compound (15.0 g, 99%) was obtained and was used without further purification. 1H NMR (500 MHz, CDCl3) delta 1.32 (t, 3H), 4.24 (q, 2H), 4.84 (dd, 2H), 6.31 (dt, 1H), 7.04 (dt, 1H), 7.18-7.26 (m, 2H), 7.80 (d, 1H). MS m/z 298 (M-H)-.

According to the analysis of related databases, 37746-78-4, the application of this compound in the production field has become more and more popular.

Reference:
Patent; ASTRAZENECA AB; O’MAHONY, Gavin; KOSSENJANS, Michael; EDMAN, Karl; KAJANUS, Johan; HOGNER, Karl Anders; CORNWALL, Philip; TURNER, Andrew; (35 pag.)US2015/376170; (2015); 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. 76008-73-6, name is Ethyl 5-bromo-2-chlorobenzoate, This compound has unique chemical properties. The synthetic route is as follows., Formula: C9H8BrClO2

Under a nitrogen atmosphere, a 50 mL round bottom flask is charged with bis(pinacolato)diborane (1.16 g, 4.55 mmol), potassium acetate (1.11 g, 11.4 mmol) and 5-bromo-2- chloro-benzoic acid ethyl ester (1 g, 3.79 mmol). After bubbling nitrogen through the mixture for 5 minutes, dichloro[l,r-bis(diphenylphosphino)ferrocene]palladium DCM adduct [PdCl2(dppf), 93 mg, 0.11 mmol] is added. The resulting mixture is heated to 60C for 2 hours, cooled to room temperature and poured into EtOAc (50 mL). This mixture is washed with water, with brine, dried over sodium sulfate, filtered and concentrated to give 2-chloro-5-(4A5,5-tetramethyl-[l . 3,2″|dioxaborolan-2-yl)- benzoic acid ethyl ester [LCMS: Rtau = 5.1 minutes, MS: 311 (M+H)] and the dimerized side product, 4,3′-Dichloro-biphenyl-3,4′-dicarboxylic acid diethyl ester in 2:1 ratio (0.65 g total). The crude mixture is used for a next step without further purification.

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 76008-73-6.

Reference:
Patent; SANOFI-AVENTIS U.S. LLC; HARRIS, Keith John; WO2008/39882; (2008); A1;,
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These common heterocyclic compound, 4891-38-7, name is Methyl Phenylpropiolate, 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. Application In Synthesis of Methyl Phenylpropiolate

EXAMPLE 24 [3,5-diphenylisoxazole-4-yl]methyl carboxylate The benzonitrile oxide (0.98 mmoles) just prepared is added to the methyl 3-phenylpropiolate (157 mg, 0.98 mmoles) in anhydrous methylene chloride (5 ml) kept stirring at ambient temperature in an atmosphere of N2. The reaction mixture is kept stirring for 12 h, then blocked by adding H2O, The phases are separated and the aqueous phase is extracted with methylene chloride. The organic phases are combined, dried with anhydrous Na2SO4 and the solvent is distilled in a vacuum. Chromatography is performed on silica gel (eluent:petroleum ether/ethyl acetate=10:1). 184 mg of product are obtained (67% yield). M.p. 102.5-104.8 C. FT-IR (KBr): 3062, 2958, 1729, 1610, 1593, 1573, 1494, 1448, 1408, 1320, 1237, 1188, 1120, 1076, 1043, 941, 806, 768, 726, 697 cm-1. 1H NMR (300 MHz, CDCl3, delta): 7.96-7.88 (m, 2H, aromatic protons); 7.70-7.63 (m, 2H, aromatic protons); 7.56-7.46 (m, 6H, aromatic protons); 3.72 (s, 3H, CH3). 13C NMR (75 MHz, CDCl3, delta): 172.7, 163.2, 163.1, 131.6, 130.2, 129.1, 128.9, 128.8, 128.7, 128.6, 127.1, 102, 52.2. GC-MS (70 eV) m/z (rel.int.): 279 (M+, 79), 278 (17), 251 (6), 220 (5), 202 (7), 143 (10), 105 (100), 77 (47), 51 (9). Anal. Calc: for C17H13NO3: C, 73.11; H, 4.69; N, 5.02. Found: C, 73.06; H, 4.67; N, 5.06.

The synthetic route of Methyl Phenylpropiolate has been constantly updated, and we look forward to future research findings.

Reference:
Patent; Scilimati, Antonio; Vitale, Paola; Di Nunno, Leonardo; Patrignani, Paola; Tacconelli, Stefania; Capone, Marta Luciana; US2009/181970; (2009); A1;,
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Electric Literature of 185312-82-7, 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 185312-82-7 as follows.

In the same manner as in Preparation Example 80-1, the objective compound (908 mg) was obtained as a colorless oil from methyl 4-bromo-2-chlorobenzoate (1 g). 1H-NMR(CDCl3): 3.91(3H, s), 4.19(2H, s), 7.15(1H, dd, J=8, 1 Hz), 7.23-7.43(6H, m), 7.75(1H, d, J=8 Hz)

According to the analysis of related databases, 185312-82-7, the application of this compound in the production field has become more and more popular.

Reference:
Patent; Fujisawa Pharmaceutical Co., Ltd.; US6348474; (2002); B1;,
Ester – Wikipedia,
Ester – an overview | ScienceDirect Topics

Synthetic Route of 685-88-1, 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. 685-88-1, name is Diethyl fluoromalonate belongs to esters-buliding-blocks compound, it is a common compound, a new synthetic route is introduced below.

NaH (0.88 g, 22 mmol 60% in mineral oil) was washed free from the oil with hexanes (3 × 10 mL) and was suspended in dry DMF (30 mL). Diethyl fluoromalonate (2.85 g, 16 mmol) dissolved in dry DMF (10 mL) was added dropwise while cooled in ice. After stirring for 10 minutes, 1-fluoro-2-nitrobenzene (2.10 g, 15 mmol) in dry DMF (10 mL) was added and the mixture was heated to 90 C for 18 hours. After cooling to room temperature, the mixture was poured into water (300 mL), acidified with concentrated HCl (2 mL) and extracted with ether (3 × 70 mL). The combined extracts were washed with saturated NaHCO3 solution (2 × 50 mL) and brine (1 × 50 mL) and dried over Na2SO4. After evaporation of the solvent under reduced pressure an orange oil was obtained that was purified by Kugelrohr distillation (8 mbar, 200 C) to afford diethyl 2-fluoro-2-(2-nitrophenyl)malonate (3, 3.21 g, 71%) as an orange solid. M.p. 48-49 C; IR (neat, cm-1) 2996, 1755, 1530, 1276, 1103; deltaH (CDCl3, 400 MHz) 1.33 (6H, t, J 7.1, CH3), 4.31 – 4.43 (4H, m, CH2), 7.57 – 7.63 (2H, m, Ar-H), 7.66 – 7.71 (1H, m, Ar-H), 8.04 (1H, d, J 8.0, Ar-H); deltaF (CDCl3, 376 MHz) – 152.98 (s, C-F); deltaC (CDCl3, 100 MHz) 14.01 (s, CH3), 63.55 (s, CH2), 94.05 (d, 1JCF 198.7, C-F), 125.87 (s, Ar), 128.54 (s, Ar), 128.66 (s, Ar), 128.89 (s, Ar), 130.97 (s, Ar), 133.30 (s, Ar), 164.68 (d, 2JCF 25.1, COO); m/z (ASAP): 226.0 (85%, [M-CO2Et]+), 134.0 (100%).

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, Diethyl fluoromalonate, other downstream synthetic routes, hurry up and to see.

Reference:
Article; Harsanyi, Antal; Sandford, Graham; Yufit, Dmitri S.; Howard, Judith A.K.; Beilstein Journal of Organic Chemistry; vol. 10; (2014); p. 1213 – 1219;,
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Application of 40546-94-9,Some common heterocyclic compound, 40546-94-9, name is 6-Methyl-4-phenylchroman-2-one, molecular formula is C16H14O2, 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 17 [0091] A solution of 0.50 g of 6-methyl-4-phenyl-2-chromanone, 2.65 g of N-fluorobenzenesulfonimide, 22 ml of THF and 6.5 ml of toluene, was cooled to -100 C., and 7.34 ml of a 1.0M THF solution of potassium hexamethyldisilazide was added. After raising the temperature to room temperature, an aqueous citric acid solution was added to terminate the reaction, followed by extraction with ethyl acetate, and the solvent was removed. 0.87 g of the obtained product was quantitatively analyzed by 19F NMR, whereby it was confirmed that 3,3-difluoro-6-methyl-4-phenyl-2-chromanone was formed in a yield of 25%. No formation of a monofluoro product was detected. The structural characteristics of the 3,3-difluoro-6-methyl-4-phenyl-2-chromanone are as follows. 19F-NMR (deuterated acetone): -96.5 (bs).

The synthetic route of 40546-94-9 has been constantly updated, and we look forward to future research findings.

Reference:
Patent; Asahi Glass Company, Limited; ISHIBASHI, Yuichiro; Matsumura, Yasushi; US2015/175632; (2015); A1;,
Ester – Wikipedia,
Ester – an overview | ScienceDirect Topics

Related Products of 35418-07-6, A common heterocyclic compound, 35418-07-6, name is Methyl 3-(4-aminophenyl)propanoate, molecular formula is C10H13NO2, 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 XXVII 1-[4-[2-(Methoxycarbonyl)ethyl]phenyl]-4,5-dimethyl-3H-imidazol-2-one 2.4 g of N-[4-[2-(methoxycarbonyl)ethyl]phenyl]-urea ?melting point: 152-154 C. (sintering from 145 C.); prepared from methyl 3-(4-aminophenyl)propionate by reacting with potassium cyanate in the presence of glacial acetic[acid]and 2.9 g of acetoin are heated to 180 C. for 1 hour under nitrogen. The reaction mixture is cooled stirred with ice water and the solid substance is suction filtered. The product is washed with water and diethylether and dried at 100 C. Yield: 1.6 g (54% of theory) Melting point: 176-181 C. Rf value: 0.11 (Silica gel; cyclohexane/ethyl acetate=2:8)

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; Karl Thomae GmbH; US5681841; (1997); A;,
Ester – Wikipedia,
Ester – an overview | ScienceDirect Topics

Related Products of 581065-95-4,Some common heterocyclic compound, 581065-95-4, name is tert-Butyl 1-amino-3,6,9,12-tetraoxapentadecan-15-oate, molecular formula is C15H31NO6, 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 2-{3-[(2-{5-[(3a5,45,6aR)-2-oxo-hexahydro- 1 H-thieno[3,4-d]i midazolidin-4- yl]pentanamido}ethyl)carbamoyl]-5-[3, 5-bis(carboxymethoxy)phenyl]phenoxy}acetic acid(Preparation 5, 20.0 mg, 29.0 pmol) dissolved in DMF (500 pL) was added HATU (44.0 mg,116 pmol) and DIPEA (40.5 pL, 232 pmol). After 1 minute tert-butyl 1-amino-3,6,9,12- tetraoxapentadecan-15-oate (35.0 pL, 116 pmol) was added and the reaction was stirred at room temperature under nitrogen for 3 hours. The reaction was concentrated in vacuo and purified using reverse phase column chromatography (Biotage SP1, 4 g, 0-18 column, elutingwith 5-40% MeCN in water with 0.1% NH3) to afford the title compound as a colourless oil (30.9 mg, 67%).LCMS Method B: Rt = 2.96 mins, ES MS mlz 599.7 [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 tert-Butyl 1-amino-3,6,9,12-tetraoxapentadecan-15-oate, its application will become more common.

Reference:
Patent; CENTAURI THERAPEUTICS LIMITED; PICKFORD, Christopher; WATSON, Christine; GLOSSOP, Melanie; (189 pag.)WO2017/60729; (2017); A1;,
Ester – Wikipedia,
Ester – an overview | ScienceDirect Topics

Application of 581065-95-4, 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. 581065-95-4, name is tert-Butyl 1-amino-3,6,9,12-tetraoxapentadecan-15-oate belongs to esters-buliding-blocks compound, it is a common compound, a new synthetic route is introduced below.

00345] tert- butyl 2-((2-(2,6-dioxopiperidin-3-yl)-l,3-dioxoisoindolin-4-yl)oxy)acetate (0775) (0.06rng, 0.13mmol) was dissolved in 1 ml. TFA. The solution was stirred at room temperature for 2 hours. Then the mixture was concentrated under reduced pressure to afford solid product, which was used in the following synthesis without further purification. Then the product from last step (0.043g, 0.13mmol) was mixed with HATH (0.099g, 0.26mmol) in 2mL DMF with the presence of EtsN (9luL, G.65mrnol). The mixture was stirred for lOmin before amino PEG-4-i-butyl ester (0.042g, O.lSmmol) was added. The reaction was stirred at room temperature for 5 hours. The mixture was next subjected to direct preparative HPLC purification to afford 97mg product (>100%) LCMS (ESI) m/z 580.22 (show as free acid instead of t-butyl ester) [(M+H)+; calcd for C^TTfiNsOii : 636.28]

The synthetic route of tert-Butyl 1-amino-3,6,9,12-tetraoxapentadecan-15-oate has been constantly updated, and we look forward to future research findings.

Reference:
Patent; DANA-FARBER CANCER INSTITUTE, INC.; BUHRLAGE, Sara; ANDERSON, Kenneth C.; HIDESHIMA, Teru; GRAY, Nathanael S.; LIU, Xiaoxi; (137 pag.)WO2019/118728; (2019); A1;,
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Ester – an overview | ScienceDirect Topics