Month: February 2021

Electric Literature of 33786-89-9, These common heterocyclic compound, 33786-89-9, name is 5-Chloro-m-phenylenediamine, 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 6 In an autoclave, 28.6 g. of 3,5-diaminochlorobenzene, 2 g. of cuprous chloride and 122 g. of 28% ammonia water were charged to react them at 165 to 170 C. for 8 hours to obtain 1,3,5-triaminobenzene. Ammonia was discharged and the product was recrystallized to obtain 19 g. of 1,3,5-triaminobenzene.

The synthetic route of 33786-89-9 has been constantly updated, and we look forward to future research findings.

Reference:
Patent; Ishihara Sangyo Kaisha Ltd.; US4380670; (1983); A;,
Chloride – Wikipedia,
Chlorides – 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. 699-89-8, name is 4,7-Dichlorothieno[2,3-d]pyridazine, A new synthetic method of this compound is introduced below., Computed Properties of C6H2Cl2N2S

A 250 mL, round-bottomed flask was equipped with a stir bar and reflux condenser. To the flask was added the product of step 4 (7.65 g, 37.3 mmol), 4-chloroaniline (4.76, 37.3 mmol) in EtOH (75 mL). The mixture was refluxed for 3 h. An orange solid precipitated from the reaction after 3 h. The reaction was cooled to rt and the solid was collected by filtration and washed with hexane. The desired 7-chloro-4-(4-chlorophenylamino)thieno[2,3-d]pyridazine was obtained (6.5 g, 21.9 mmol; 60% yield); mp= 139-142 C; ES MS (M+H)+= 297; TLC (Hexane- EtOAc, 60:40); Rf = 0.48.; To the dichloride from Example 8, step 4 (1.00 g, 4.90 mmol) was added p-chloroaniline (622 mg, 4.90 mmol) and absolute ethyl alcohol (10.0 mL). The mixture was refluxed at 95 C for 2 hrs and then cooled to room temperature. The yellow precipitate (2) that formed was filtered and washed with isopropyl alcohol, 4.0 N KOH, H2O, and then hexane. The filtrate (2) was then mixed 6-aminobenzothiazole (883 mg, 5.88 mmol) in 10 mL of n-butanol, and heated at 150 C overnight. The reaction was allowed to cool to room temperature before the solvent was removed by rotary evaporation. The residue was treated sequentially with aqueous 4.0 N KOH solution and extracted with dichloromethane (50 mL), dried (MgSO4), and the solvent evaporated. The crude product was purified by flash chromatography on silica gel using 95% dichloromethane/methanol as the eluent. The structure of the pure title compound was confirmed by LC/MS and NMR: TLC (30% EtOAc/Hexanes) Rf (3) = 0.20; 1H NMR (DMSO) delta 7.2 (dd, 3H), 7.38 (dd, 3H), 7.65 (d, 1H), 8.0 (d, 1H), 8.45 (d, 1H), 8.8 (s, 1H); LC/MS m/z 410 rt = 4.21 min.; Equal equivalents of dichloride (1) and M-NH2 are refluxed in the appropriate amount of absolute ethanol at 95 C for 2 hrs. The reaction mixture is allowed to cool to room temperature and the precipitate (2) that forms is filtered and washed sequentially with isopropyl alcohol, 4.0 N KOH, H2O, and hexane, and then dried. The filtrate (2) is then reacted with 1.2 equivalent of Q-NH2 in an appropriate amount of n-butyl alcohol at 150 C for 10 hrs. The reaction is cooled to room temperature before the solvent is evaporated under reduced pressure. The residue is treated with aqueous 4.0 N KOH solution and extracted with dichloromethane. The organic layer is dried (MgSO4) and evaporated. The crude product (3) is purified by preparative thin layer chromatography (TLC) or flash chromatography on silica gel using dichloromethane/methanol (95:5) as the eluent. Final product is confirmed by LC/MS and/or NMR. The invention compounds of Examples 23 – 25, 48, and 76-80 as shown in the below table were prepared by method A-1.

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; BAYER CORPORATION; EP1228063; (2009); B1;,
Chloride – Wikipedia,
Chlorides – an overview | ScienceDirect Topics

Adding a certain compound to certain chemical reactions, such as: 106131-61-7, name is 3,6-Dichloro-1,2,4,5-tetrazine, belongs to chlorides-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 106131-61-7, Application In Synthesis of 3,6-Dichloro-1,2,4,5-tetrazine

General procedure: In a 100 mL round bottom flask, was introduced the diol(0.33 mmol), s-collidine (0.39 mmol) and 20 mL of dry dichloromethane and the mixture was stirred at room temperature. 3,6-dichloro-s-tetrazine 1 (0.66 mmol) was dissolved in dry dichloromethane and added dropwise in the flask. After2 h the reaction is complete (TLC) and the solvent removed under reduced pressure. The crude residue was purified by column chromatography on silica gel (eluent petroleumether/ethyl acetate 1/1).

At the same time, in my other blogs, there are other synthetic methods of this type of compound, 3,6-Dichloro-1,2,4,5-tetrazine, and friends who are interested can also refer to it.

Reference:
Article; Guermazi, Refka; Royer, Lorna; Galmiche, Laurent; Clavier, Gilles; Audebert, Pierre; Hedhli, Ahmed; Journal of Fluorescence; vol. 26; 4; (2016); p. 1349 – 1356;,
Chloride – Wikipedia,
Chlorides – an overview | ScienceDirect Topics

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. 1303587-99-6, name is 2-Chloro-7,8-dihydro-6H-pyrimido[5,4-b][1,4]oxazine belongs to chlorides-buliding-blocks compound, it is a common compound, a new synthetic route is introduced below. category: chlorides-buliding-blocks

Synthesis of2-chloro-8-(l-phenylethyl)-7, 8-dihydro-6H-pyrimido [5, 4-b] [I, 4] oxazine [0454] To a stirred solution of 2-chloro-7, 8-dihydro-6H-pyrimido [5, 4-b] [1, 4] oxazine (100 mg, 0.58 mmol) in DMF (2 mL) under argon atmosphere was added sodium hydride (27 mg, 1.16 mmol) at 0 C. After stirring for 10 mins, (1-bromoethyl) benzene (130 mg, 0.70 mmol) was added to the reaction mixture at 0 C and stirred for 1 h. After consumption of the starting materials (monitored by TLC), the reaction was diluted with water (20 mL) and extracted with EtOAc (2 x 20 mL). The combined organic extracts were dried over sodium sulfate, filtered and concentrated in vacuo to afford 2-chloro-8-(l-phenylethyl)-7, 8-dihydro- 6H-pyrimido [5, 4-b] [1, 4] oxazine (140 mg, 87%) as an off-white solid. 1H-NMR (CD3OD, 400 MHz): delta 7.60 (s, 1H), 7.39-7.23 (m, 5H), 6.20-6.11 (m, 1H), 4.18-4.10 (m, 1H), 3.98- 3.91 (m, 1H), 3.50-3.41 (m, 1H), 3.10-3.02 (m, 1H), 1.60 (s, 3H); LCMS: 275.8 (M+l); (column; X-Select CSH C-18 (50 3.0 mm, 3.5 mupiiota); RT 3.70 min 0.05% Aq TFA: ACN; 0.80 mL/min); TLC: 60% EtOAc/hexane (R 0.5).

The synthetic route of 1303587-99-6 has been constantly updated, and we look forward to future research findings.

Reference:
Patent; FORUM PHARMACEUTICALS INC.; BURNETT, Duane, A.; BURSAVICH, Matthew, Gregory; MCRINER, Andrew, J.; WO2015/66697; (2015); A1;,
Chloride – Wikipedia,
Chlorides – an overview | ScienceDirect Topics

Reference of 1435-48-9, 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. 1435-48-9, name is 2,4-Dichloro-1-fluorobenzene, This compound has unique chemical properties. The synthetic route is as follows.

To a suspension of 60% sodium hydride (2.00 g) in DMF (25 mL) was added dropwise a solution of tert-butyl4-(hydroxymethyl)piperidine-1-carboxylate (8.00 g) in DMF (25 mL) at 0C, and then 2,4-dichloro-1-fluorobenzene (4.38mL) was added thereto. The reaction mixture was stirred at room temperature for 18 hr. To the reaction mixture wereadded water and aqueous ammonium chloride solution, and the mixture was extracted with ethyl acetate. The organiclayer was washed with saturated brine, dried over anhydrous magnesium sulfate, and concentrated under reducedpressure. The residue was purified by silica gel column chromatography (ethyl acetate/hexane) to give tert-butyl 4-((2,4-dichlorophenoxy)methyl)piperidine-1-carboxylate as a crude product.

The chemical industry reduces the impact on the environment during synthesis 2,4-Dichloro-1-fluorobenzene. I believe this compound will play a more active role in future production and life.

Reference:
Patent; Takeda Pharmaceutical Company Limited; IKEDA, Shuhei; KOIKE, Tatsuki; AIDA, Jumpei; FUSHIMI, Makoto; KUSUMOTO, Tomokazu; SUGIYAMA, Hideyuki; MIYAZAKI, Masako; TOKUHARA, Hidekazu; HATTORI, Yasushi; KAMATA, Makoto; (149 pag.)EP3279191; (2018); A1;,
Chloride – Wikipedia,
Chlorides – an overview | ScienceDirect Topics

These common heterocyclic compound, 1939-99-7, name is Phenylmethanesulfonyl chloride, 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 Phenylmethanesulfonyl chloride

K2CO3 (8.7 g, 62 mmol) was added into a mixture of phenylmethanesulfonyl chloride (6 g, 31 mmol) and 2-bromoethanamine hydrobromide (6.4 g, 31 mmol) in DCM (100mL) at 0C. And the resulting mixture was stirred at r.t. for 4 hours and left standing overnight. Upon the completion of reaction, water (100 mL) was added in and DCM phase was separated.The aqueous phase was extracted with DCM. The combined organic phase was dried over Na2SO4, filetered and concentrated in vacuo to provide a crude which was separated with column chromatography (silica gel with 200 – 300 mesh, 0 to 50% of EtOAc in petroleum ether) to provide compound N-(2-bromoethyl)(phenyl)methanesulfonamide (7.0 g, 80%) as a pale yellow solid. 1H NMR (300 MHz, CDCl3) delta 7.40 (m, 5H), 4.58 (m, 1H), 4.29 (s, 2H), 3.34-3.29 (m, 4H). LCMS (ESI), 300, 302 [M+Na]+ , Br pattern found.

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

Reference:
Patent; F. HOFFMANN-LA ROCHE AG; GENENTECH, INC.; FAUBER, Benjamin; RENE, Olivier; (86 pag.)WO2017/102796; (2017); A1;,
Chloride – Wikipedia,
Chlorides – an overview | ScienceDirect Topics

Adding a certain compound to certain chemical reactions, such as: 1435-50-3, name is 2-Bromo-1,4-dichlorobenzene, belongs to chlorides-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 1435-50-3, Computed Properties of C6H3BrCl2

EXAMPLE 1 To a 300 ml four-necked flask equipped with a stirrer, a thermometer and a condenser were charged 24.9 g (0.110 mol) of 1-bromo-2,5-dichlorobenzene, 13.19 g (0.143 mol) of thioglycolic acid, 12.06 g (0.286 mol) of 95% sodium hydroxide and 100 g of dimethylsulfoxide, followed by stirring at 120 C. for 4 hours. Then, after distilling off the dimethylsulfoxide under reduced pressure, 100 g of water was added to the residue. After dissolving the residue therein at 100 C., the solution was cooled for crystallization and filtered to yield sodium 2,5-dichlorophenylthioglycolate, which was then dissolved in 100 g of water with heating and acidized with concentrated hydrochloric acid, filtered and dried to yield 19.6 g of a light yellowish white powder of 2,5-dichlorophenylthioglycolic acid.

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; Sumitomo Seika Chemicals Co., Ltd.; US5210291; (1993); A;,
Chloride – Wikipedia,
Chlorides – an overview | ScienceDirect Topics

Reference of 16817-43-9, 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 16817-43-9 as follows.

General procedure: To a flame-dried 25 mL round bottom flask was charged activated Mg (7.5 mmol, 1.5 eq.) and 5 mL anhydrous THF. To this suspension was added 2 drops of 1,2-dibromoethane. After 5 min, a solution of Aryl bromide (5 mmol, 1.0 eq.) in 5 mL anhydrous THF was slowly added to the suspension of Mg at room temperature. The reaction was mildly exothermic. The Grignard reagent was titrated and 1 mmol of this reagent was added to a flame-dried reaction vial. The solution was diluted with 3 mL anhydrous toluene and after cooling to the target temperature T, a solution of oxaziridine (1.2 mmol, 1.2 eq.) in 1 mL anhydrous toluene was added. The reaction was maintained at the targeted temperature T for time t before being quenched with saturated aqueous NH4Cl. (The actual temperature/reaction time is listed for each substrate.)

According to the analysis of related databases, 16817-43-9, the application of this compound in the production field has become more and more popular.

Reference:
Patent; WILLIAM MARSH RICE UNIVERSITY; GAO, HONGYIN; ZHOU, Zhe; KURTI, Laszlo; (51 pag.)US2018/57444; (2018); 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. 2613-32-3, name is 2-Chloro-4,5-difluoroaniline, This compound has unique chemical properties. The synthetic route is as follows., Recommanded Product: 2-Chloro-4,5-difluoroaniline

[ithium 1,1,1 ,3,3,3-hexamethyldisilazan-2-ide (42 ml, 1 M solution in tetrahydrofuran, 42 mmol, CAS No 4039-32-1) was added drop wise within 5 minutes to a solution of 2-chloro- 4,5-difluoroaniline (3.88 g, 23.2 mmol) in tetrahydrofuran (110 ml) at -780 and the mixture was stirred for 1 h at that temperature. A solution of ethyl 4-{[tert-butyl(diphenyl)silyl]oxy}-1 – (2-chloroethyl)cyclohexanecarboxylate (10.0 g, 21.1 mmol) in tetrahydrofuran (110 ml) wasadded and the mixture was stirred for 2 h at -78G. The mixture was warmed to room temperature and stirred for 4 d. For work-up, the reaction mixture was added to a mixture of water and sodium bicarbonate solution and the mixture was extracted with ethyl acetate (3x). The combined organic phases were washed with sodium chloride, dried over sodium sulfate and concentrated under reduced pressure, the residue was purified by flash chromatography (340 g Snap cartridge, hexane/ethyl acetate gradient, 5% -> 25% ethyl acetate). The productcontaining fractions were concentrated and were purified a second time by flash chromatography (120 g Snap cartridge, hexane/ethyl acetate gradient, 5% -> 25% ethyl acetate) to give the title compound in 2 fractions: fraction 1 (7.53 g, single isomer based on 1H NMR, isomer 1, contains impurities from aniline and isomer 2), fraction 2(1.13 g, isomer2).Fraction 1 (isomer 1): 1H-NMR (400 MHz, DMSO-d6): 6 [ppm] = 7.67-7.55 (m, 5H), 7.52-7.30 (m, 9H), 3.97 (brs, 1H), 3.60 (t, 2H), 2.15-2.07 (m, 2H), 2.04 (t, 2H), 1.76-1.63 (m, 2H), 1.58- 1.45 (m, 2H), 1.39-1.27 (m, 2H), 1.05 (5, 9H).[C-MS (Method 1): R = 1.80 mm; MS (ESIpos): m/z = 518.3 [M¡ÂH]

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 2613-32-3.

Reference:
Patent; BAYER PHARMA AKTIENGESELLSCHAFT; EIS, Knut; ACKERMANN, Jens; WAGNER, Sarah; BUCHGRABER, Philipp; SUeLZLE, Detlev; HOLTON, Simon; BENDER, Eckhard; LI, Volkhart; LIU, Ningshu; SIEGEL, Franziska; LIENAU, Philip; BAIRLEIN, Michaela; VON NUSSBAUM, Franz; HERBERT,Simon; KOPPITZ, Marcus; (734 pag.)WO2016/177658; (2016); A1;,
Chloride – Wikipedia,
Chlorides – an overview | ScienceDirect Topics

Electric Literature of 74483-46-8, These common heterocyclic compound, 74483-46-8, name is 2-Chloro-4-methyl-1-(trifluoromethyl)benzene, 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: 3-Chloro-4-trifluoromethylbenzylbromide 27 A mixture of 2-chloro-4-methyl-1-trifluoromethylbenzene 26 (0.20 g, 1 mmol), N-bromosuccinimide (0.17 g, 1 mmol) and benzoyl peroxide (7.4 mg, 0.03 mmol) in carbon tetrachloride (2 mL) was heated to reflux for 2 hours. Another portion of benzoyl peroxide (20 mg, 0.08 mmol) was added. The mixture was heated to reflux for another 0.5 hours. The reaction mixture was further stirred at room temperature for 16 hours. The solid was removed by filtration. The solvent was removed under reduced pressure. The crude product was purified by flash chromatography on silica, using petroleum ether as eluent, to give 0.22 g (80%) of Compound 27.

Statistics shows that 2-Chloro-4-methyl-1-(trifluoromethyl)benzene is playing an increasingly important role. we look forward to future research findings about 74483-46-8.

Reference:
Patent; CanBas Co., Ltd.; US2008/275057; (2008); A1;,
Chloride – Wikipedia,
Chlorides – an overview | ScienceDirect Topics