Month: November 2020

Some common heterocyclic compound, 50638-46-5, name is 4-Bromo-3-chloroanisole, molecular formula is C7H6BrClO, 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. 50638-46-5

Step 1; Scheme 30:; To a mixture of 4-bromo-3-chloro anisole (35 g, 0.159 mol), KCl (11.9 g, 0.160 mol, 1 eq.), K2CO3 (33 g, 0.238 mol, 1.5 eq) in 400 mL DMF in a sealed tube was added acrolein diethylacetal (73 mL, 0.479 mol, 3 eq.) and Bu4NOAc (96 g, 0.318 mol, 2 eq.). N2 was bubbled through the mixture and Pd(OAc)2 (1.1 g, 4. mmol, 3 mol %) was added. The reaction mixture was heated in an oil bath for 6 hr at 100 C. then cooled in an ice-bath. 300 mL of water was then added, followed by 500 mL of 1N HCl. The ice-bath was removed and the mixture was stirred for 30 min. The solution was extracted with ethyl acetate once then with diethyl ether 3 times. The combined organic layer washed with water, brine, dried over MgSO4, filtered and concentrated to provide the crude product which was recrystallized from hot ethyl acetate-hexanes to provide 15.5 g of crystalline 3-(2-chloro-4-methoxy-phenyl)-propenal. The mother liquor was concentrated and chromatographed with 10% ethyl acetate to provide another 5.6 g of 3-(2-chloro-4-methoxy-phenyl)-propenal.

These compound has a wide range of applications. It is believed that with the continuous development of the source of the synthetic route 50638-46-5, its application will become more common.

Reference:
Patent; Chackalamannil, Samuel; Chelliah, Mariappan V.; Clasby, Martin C.; Eagen, Keith A.; Scott, Jack D.; Wang, Yuguang; Xia, Yan; Greenlee, William J.; US2007/197628; (2007); A1;,
Chloride – Wikipedia,
Chlorides – an overview | ScienceDirect Topics

A common heterocyclic compound, 108-70-3, name is 1,3,5-Trichlorobenzene, molecular formula is C6H3Cl3, 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. 108-70-3.

General procedure: Palladium(II) acetate (0.025 mmol, 5.6 mg), XPhos (0.0375 mmol, 17.9 mg), and phenylsilatrane (2a, 0.75 mmol, 188.5 mg) were added to a Schlenk flask. The flask was then purged with nitrogen. 4-Chloroanisole (1a) (0.50mmol, 71.3 mg), toluene (1.5 mL), and TBAF (0.75 mmol, 0.75 mL in ca. 1.0 M THF solution) were subsequently added. The mixture was stirred at 100 C for 3 h, then quenched by addition of water, and extracted with EtOAc. The organic layer was washed with brine, dried over anhydrous Na2SO4, filtered,and concentrated in vacuo. The crude product was purified by flash column chromatography on silica gel (hexane) to provide 3a (75.2 mg, 0.408 mmol) in 82% yield.

The synthetic route of 1,3,5-Trichlorobenzene has been constantly updated, and we look forward to future research findings.

Reference:
Article; Yamamoto, Yutaro; Baralle, Alexandre; Godefroy, Anais; Murakami, Kei; Yorimitsu, Hideki; Osuka, Atsuhiro; Heterocycles; vol. 95; 1; (2017); p. 568 – 574;,
Chloride – Wikipedia,
Chlorides – an overview | ScienceDirect Topics

108-37-2, A common compound: 108-37-2, name is 1-Bromo-3-chlorobenzene, belongs to chlorides-buliding-blocks compound, it can change the direction of chemical reaction, and react with certain compounds to generate new functional products. A new synthetic method of this compound is introduced below.

General procedure: A mixture of aryl halide (1 mmol), phenyltributyltin (1.2 mmol), K2CO3 (1 mmol), and ortho-palladated catalyst (0.3 mol %) in DMF (2 mL) in a round-bottom flask equipped with a condenser was placed into a Milestone microwave reactor. Initially using a microwave power of 500 W, the temperature was ramped from room temperature to 90 C, (ca. 1 min), and then held at this temperature until the reaction was complete. During this time, the power was modulated automatically to keep the reaction mixture at 90 C. The mixture was stirred continuously using an appropriate magnet during the reaction. After the reaction was complete, the mixture was cooled to room temperature and diluted with H2O (30 ml) and Et2O (30 ml). The organic phase was washed with saturated KF solution (30 ml), and dried over MgSO4. The solution was filtered and the solvent evaporated using a rotary evaporator. The residue was purified by silica gel column chromatography [n-hexane or n-hexane/EtOAc (9:1)].

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, 1-Bromo-3-chlorobenzene, other downstream synthetic routes, hurry up and to see.

Reference:
Article; Hajipour, Abdol Reza; Rafiee, Fatemeh; Tetrahedron Letters; vol. 53; 35; (2012); p. 4661 – 4664;,
Chloride – Wikipedia,
Chlorides – an overview | ScienceDirect Topics

344-19-4, 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 344-19-4 as follows.

2,6-dichloro-4-fluoro-aniline (12 g, 67 mmol) was taken up in concentrated H0I (13 mL)and water (Si mL) at 0 00 After stirring for iS mm, a solution of NaNO2 (4.85 g, 70.3 mmol) in 147water (10 mL) was added drop-wise at 0 00 and the mixture was stirred for 45 mm. A solution of MeSNa (35 g, 100 mmol) and Na2CO3 (10.6 g, 100 mmol) in water (100 mL) was then added to the above solution drop-wise at 50 00. After addition, the mixture was stirred for 1 hour, then extracted with Et0Ac and the combined organic layers were dried (MgS04), filtered and thefiltrate concentrated in vacuo to give the crude product. Flash chromatography using neat 60-90 petrol ether afforded 1 ,3-d ichloro-5-fluoro-2-methylsulfanyl-benzene (4.7 g, 34%).1H NMR (ODd3, 400MHz): 57.17 (d, 2H), 2.41 (s, 3H).

According to the analysis of related databases, 2,6-Dichloro-4-fluoroaniline, the application of this compound in the production field has become more and more popular.

Reference:
Patent; BASF SE; CALO, Frederick; KORDES, Markus; KRAUS, Helmut; MIETZNER, Thomas; SEITZ, Thomas; KREUZ, Klaus; PASTERNAK, Maciej; NEWTON, Trevor William; MASSA, Dario; WO2015/7564; (2015); A1;,
Chloride – Wikipedia,
Chlorides – an overview | ScienceDirect Topics

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. 6940-78-9, name is 1-Bromo-4-chlorobutane, This compound has unique chemical properties. The synthetic route is as follows., 6940-78-9

A. Preparation of the intermediate compounds; Example AlA; a) Preparation of intermediate 1; To a stirred solution of Grignard reagent at 5C, prepared from Mg turnings (0.14 mol) and l-bromo-4-chlorobutane (0.14 mol) in diethylether (150 ml), was added dropwise a solution of 2-naphthylcarboxaldehyde (0.0935 mol) in TEtaF (150 ml). After the mixture was stirred for 4 hours at 5C a solution of ammonium chloride (10% aqueous) was added slowly. The organic layer was separated, washed with brine, dried over EPO magnesium sulfate, filtered, and the solvent was evaporated. The residue was purified by column chromatography over silica gel (eluent: cyclohexane/EtOAc : 90/10 ; 15-40 mum). The pure fractions were collected and the solvent was evaporated. Yield : 8.2 g of intermediate 1 (35%).

If you are interested in these compounds, you can also browse my other articles.Thank you for taking the time to read this article. I hope you enjoyed it.

Reference:
Patent; JANSSEN PHARMACEUTICA N.V.; WO2007/435; (2007); A1;,
Chloride – Wikipedia,
Chlorides – an overview | ScienceDirect Topics

6940-78-9, A common heterocyclic compound, 6940-78-9, name is 1-Bromo-4-chlorobutane, molecular formula is C4H8BrCl, 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.

NaH (0.31 g, 7.7 mmol, 2.0 eq.,60% in mineral oil) was washed three times with 5 mL of n-hexane. The suspension was decanted after each wash and n-hexane traces were removed under reduced pressure. Anhydrous DMF (15 mL) was then added and the suspension was stirred for 5 min. A solution of 1,2,5,6-Di-O-isopropylidene-alpha-D-glucofuranose (4, 1.00 g, 3.8 mmol, 1.0 eq.) in anhydrous DMF (15 mL) was then added dropwise. After stirring for 30 min under nitrogen flow, a solution of 1-bromo-4-chlorobutane (2.63 g, 15.4 mmol,4.0 eq.) in anhydrous DMF (5 mL) was added dropwise and the mixture was vigorously stirred for 24 hours at 40 C. The reaction mixture was then diluted in CH2Cl2 (150 mL) and washed with 0.3 N HCl (5 ¡Á 100 mL). The organic layer was dried over MgSO4 and filtered. The solvent was evaporated under reduced pressure and the residue was purified by column chromatography (CH2Cl2:EtOAc 9:1) to give 5 (0.81 g, 60% yield) as a pale yellow oil. 1H-NMR (CDCl3) delta (ppm) = 5.87 (d, J = 3.7 Hz, 1H, -CH-),4.53 (d, J = 3.8 Hz, 1H, -CH-), 4.32-4.24 (m, 1H, -CH-), 4.12-4.06 (m, 2H, -CH2-), 4.00-3.95 (m, 1H,-CH-), 3.86-3.44 (m, 5H, -CH-, -O-CH2-, -CH2-Cl), 1.84-1.60 (m, 4H, -CH2-CH2-), 1.49, 1.41, 1.34,1.31 (4 s, 12H, 4 ¡Á -CH3); 13C-NMR (CDCl3) delta (ppm) = 111.76, 108.98, 105.25, 83.05, 82.12, 81.21,72.34, 69.54, 67.39, 44.76, 29.26, 26.99, 26.80, 26.77, 26.21, 25.34; ESI-MS (ion trap): m/z 351 [M+H]+. Anal. calcd. for C16H27ClO6: C, 54.78; H, 7.76 Found: C, 54.69; H, 7.71.

The synthetic route of 6940-78-9 has been constantly updated, and we look forward to future research findings.

Reference:
Article; Mattarei, Andrea; Carraro, Massimo; Azzolini, Michele; Paradisi, Cristina; Zoratti, Mario; Biasutto, Lucia; Molecules; vol. 19; 10; (2014); p. 15900 – 15917;,
Chloride – Wikipedia,
Chlorides – an overview | ScienceDirect Topics

These common heterocyclic compound, 445-14-7, name is 2-Amino-4-chlorobenzotrifluoride, 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. 445-14-7

a) 5-chloro-2-(trifluoromethyl)benzene-1-sulfonyl Chloride Thionyl chloride (2 mL) was added dropwise to ice-cooled water (12 mL), and the mixture was stirred at 0 C. for 3 hr. To this solution was added copper(I) chloride (28 mg) to give solution A. To the ice-cooled concentrated hydrochloric acid (3 mL) was added 5-chloro-2-(trifluoromethyl)aniline (500 mg), and the mixture was stirred at 0 C. for 10 min. To the obtained mixture was added dropwise a solution of sodium nitrite (210 mg) in water (0.8 mL) at 0 C., and the mixture was stirred at 0 C. for 10 min. The obtained mixture was added dropwise to solution A at 0 C., and the mixture was stirred at 0 C. for 1 hr. To the reaction mixture was added water, and the mixture was extracted with ethyl acetate. The obtained organic layer was washed with water and saturated brine, dried over magnesium sulfate and concentrated to give the title compound (663 mg). 1H NMR (300 MHz, DMSO-d6) delta 7.56-7.64 (1H, m), 7.68-7.76 (1H, m), 8.04 (1H, d, J=2.4 Hz).

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 445-14-7.

Reference:
Patent; Takeda Pharmaceutical Company Limited; FUJIMOTO, Jun; LIU, Xin; KURASAWA, Osamu; TAKAGI, Terufumi; CARY, Douglas Robert; BANNO, Hiroshi; ASANO, Yasutomi; KOJIMA, Takuto; (159 pag.)US2019/169166; (2019); A1;,
Chloride – Wikipedia,
Chlorides – an overview | ScienceDirect Topics

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. 26487-67-2, name is 1-(2-Chloroethyl)azepane hydrochloride, This compound has unique chemical properties. The synthetic route is as follows., 26487-67-2

To a solution of 1,1-bis(4-hydroxyphenyl)-2-phenylbut-1-ene (26.4 mg, 83.4 mumol) in DMF (0.83 mL) at 0 ¡ãC was added 55percent sodium hydride (dispersion in paraffin liquid, 29.1 mg, 0.667 mmol). The reaction mixture was stirred for 15 min at 50 ¡ãC and then N-(2-chloroethyl)hexahydro-1H-azepine hydrochloride (54.5 mg, 0.275 mmol) was added in portions at room temperature. After the reaction mixture had been stirred for 3.5 h at 50 ¡ãC, saturated aqueous ammonium chloride was added at 0 ¡ãC. The mixture was extracted with dichloromethane and the organic layer was dried over sodium sulfate. After filtration of the mixture and evaporation of the solvent, the crude product was purified by thin layer chromatography on silica (eluant; ammoniacal chloroform/methanol = 15/1) to afford RID-F (compound 6) (37.3 mg, 79percent) as a pale yellow oil

If you are interested in these compounds, you can also browse my other articles.Thank you for taking the time to read this article. I hope you enjoyed it.

Reference:
Article; Hasegawa, Makoto; Yasuda, Yukari; Tanaka, Makoto; Nakata, Kenya; Umeda, Eri; Wang, Yanwen; Watanabe, Chihiro; Uetake, Shoko; Kunoh, Tatsuki; Shionyu, Masafumi; Sasaki, Ryuzo; Shiina, Isamu; Mizukami, Tamio; European Journal of Medicinal Chemistry; vol. 71; (2014); p. 290 – 305;,
Chloride – Wikipedia,
Chlorides – an overview | ScienceDirect Topics

27139-97-5, 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. 27139-97-5, name is 2-Bromo-4-chloro-1-methylbenzene, A new synthetic method of this compound is introduced below.

Step 1 Ethyl (E)-3-(5-chloro-2-methylphenyl)-2-propenoate To 2-bromo-4-chloro toluene (20.0 g; 97.3 mmol) in 300 mL of THF at -78¡ã C. was added n-BuLi 2.5M (40.8 mL) dropwise. After 20 min. 1-formylpiperidine (11.4 mL; 103.0 mmol) in 10 mL of THF was added dropwise. After 30 min the reaction mixture was brought to 0¡ã C. and quenched with HCl (10percent) and diluted with EtOAc. The organic phase was collected, dry and the solvent evaporated to yield 13.3 g (89percent) of 5-chloro-2-methylbenzaldehyde.

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; Merck Frosst Canada & Co.; US6242493; (2001); B1;,
Chloride – Wikipedia,
Chlorides – an overview | ScienceDirect Topics

4863-91-6, Name is 3-Chloro-5-fluoroaniline, 4863-91-6, belongs to chlorides-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.

To a cooled (0 C) solution of 3-chloro-5-fluoroaniline (5.0 g, 33 mmol) in MeCN (50 ml) was added a suspension of N-bromosuccinimide (5.9 g, 33 mmol) in MeCN (10 ml). After being stirred for 2 h at RT the reaction was quenched by adding 10 % NaHS03 (50 ml). The mixture was concentrated to about half of the volume, diluted with water (50 ml) and extracted with EtOAc (3×50 ml). Combined organic phases were dried over Na2S04 and evaporated to give crude product, which was purified by CombiFlash (column: silica, eluent: 0-100 % EtOAc in heptane) to yield 5.5 g (74 %) of the title compound. -NMR (400MHz; d6-DMSO): delta 5.88 (bs, 2H), 6.45 (dd, IH), 6.64 (m, IH).

Statistics shows that 3-Chloro-5-fluoroaniline is playing an increasingly important role. we look forward to future research findings about 4863-91-6.

Reference:
Patent; ORION CORPORATION; WOHLFAHRT, Gerd; TOeRMAeKANGAS, Olli; SALO, Harri; HOeGLUNG, Lisa; KARJALAINEN, Arja; KNUUTTILA, Pia; HOLM, Patrick; RASKU, Sirpa; VESALAINEN, Anniina; WO2011/51540; (2011); A1;,
Chloride – Wikipedia,
Chlorides – an overview | ScienceDirect Topics