Category: chlorides-buliding-blocks

Some common heterocyclic compound, 51419-59-1, name is p-Tolylmethanesulfonyl chloride, molecular formula is C8H9ClO2S, 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. HPLC of Formula: C8H9ClO2S

To a solution of 6-Amino-l-ethyl-4-methyl-4H-3,l-benzoxazin-2-one (0.140 g, 0.678 mmol) in ethyl acetate (5 mL) was added NN-diisopropylethylamine (0.175 g, 1.35 mmol) and p-tolylmethanesulfonyl chloride (0.180 g, 0.882 mmol). The reaction mixture was stirred for 15 min, concentrated and purified by flash chromatography to give the desired product as a pale solid (54 mg, 21 percent). LCMS : 0.92 min; ES+ 375 (M+H+); lH NMR (CHLOROFORM-d, 400MHz): delta (ppm) 7.12-7.20 (m, 4H), 7.09 (d, IH), 6.92 (d,lH), 6.89 (s, IH), 6.65 (s, IH), 5.29 (q, lH), 4.28 (s, 2H), 3.95 (q, 2H), 2.34 (s, 3H), 1.63 (d, 3H), 1.34 (t, 3H)

These compound has a wide range of applications. It is believed that with the continuous development of the source of the synthetic route 51419-59-1, its application will become more common.

Reference:
Patent; THE REGENTS OF THE UNIVERSITY OF CALIFORNIA; SYNGENTA PARTICIPATIONS AG; CUTLER, Sean, R.; LACHIA, Mathilde, Denise; WENDEBORN, Sebastian, Volker; GODFREY, Christopher, Richard Ayles; SABBADIN, Davide; (82 pag.)WO2018/17490; (2018); A1;,
Chloride – Wikipedia,
Chlorides – an overview | ScienceDirect Topics

Related Products of 1939-99-7, A common heterocyclic compound, 1939-99-7, name is Phenylmethanesulfonyl chloride, molecular formula is C7H7ClO2S, 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.

Ethyl piperidine-2-carboxylate (100mg, 0.63 mmol) was dissolved in 5mL of anhydrous DMF, and triethylamine (191mg, 1.89 mmol) was added drop wise followed by phenylmethanesulfonyl chloride (119.7mg, 0.63 mmol). The reaction was stirred for 6h at RT and subsequently the solvent was removed in vacuo. The crude mixture was purified using column chromatography (hexane : EtOAc 8:2) to yield Ethyl 1-(benzylsulfonyl)piperidine-2-carboxylate_(170mg, 0.55 mmol, 86%). TLC (hexane: EtOAc 8:2): Rf = 0.20. HPLC (gradient A) retention time= 23.4-23.8 min 1HNMR (300 MHz, CDCl3) delta= 1.14-1.25 (m, 1H), 1.28 (t, 3H, J= 7.2 Hz), 1.34-1.49 (m, 1H), 1.54-1.68 (m, 3H), 2.14 (d, 1H, J= 13.5 Hz), 3.14 (dt, 1H, J= 3.3, 12.6 Hz), 3.44 (d, 1H, J= 12.6 Hz), 4.18-4.24 (m, 2H), 4.26 (s, 2H), 4.54 (d, 1H, J= 4.8 Hz), 7.31-7.38 (m, 3H), 7.43-7.48 (m, 2H). 13C NMR (75 MHz, CDCl3) delta= 14.22, 20.31, 25.04, 27.78, 43.39, 55.95, 58.71, 61.36, 128.40, 128.48, 129.35, 130.96, 171.38. MS (ESI) m/z: found Rt 14.28 min. (Method LCMS), 312.12 [M + H]+, 334.22 [M + Na]+. calculated 312.12 [M + H]+, 334.11 [M + Na]+.

The synthetic route of 1939-99-7 has been constantly updated, and we look forward to future research findings.

Reference:
Patent; Max-Planck-Gesellschaft zur Foerderung der Wissenschaften e.V.; Gopalakrishnan, Ranganath; Hausch, Felix; EP2610245; (2013); A1;,
Chloride – Wikipedia,
Chlorides – an overview | ScienceDirect Topics

Reference of 118-69-4, 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 118-69-4 as follows.

Example 1Preparation of DCDNTTo a 1 L 3-neck round bottom flask equipped with external ice cooling, mechanical stirrer, addition funnel, N2 inlet, and thermometer was added 174 g (2.76 mol) fuming nitric acid (d=1.54), followed by 350 g sulfuric acid and 659 g 30% oleum (2.0 molar equiv SO3) maintaining a temperature between 5 and 20 C. Subsequently, 199 g (1.23 mol) 1,3-dichlorotoluene (99% purity, Aldrich Chemical Company, Milwaukee, Wis., USA) was added over a time period of 3 h while maintaining a temperature between 0 C.-10 C. The ice bath was removed, and the reaction mixture was allowed to warm up to room temperature. It was then heated to 100 C. for about 2 h. To analyze the reaction mixture, a small sample of crude product was taken from the reaction vessel and poured into ice water. The crude product was extracted with methylene chloride. Analysis by GC indicated a reaction selectivity to 3,5-dinitro-2,6-dichlorotoluene of >97%. Subsequently, the reaction mixture was allowed to cool to room temperature over 2 h and then cooled to 5 C. over 30 min, after which it was filtered through a glass fritted funnel and washed with a little sulfuric acid followed by 200 mL H20. The wet cake contained about 20% water. After drying, 291 g of >99.5% pure DCDNT product (by 1H-NMR) was isolated (93.5% net yield).

According to the analysis of related databases, 118-69-4, the application of this compound in the production field has become more and more popular.

Reference:
Patent; E. I. DU PONT DE NEMOURS AND COMPANY; US2010/160685; (2010); A1;,
Chloride – Wikipedia,
Chlorides – an overview | ScienceDirect Topics

Synthetic Route of 41965-95-1,Some common heterocyclic compound, 41965-95-1, name is 3-Chloro-4-methoxybenzylamine Hydrochloride, molecular formula is C8H11Cl2NO, 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.

N,N-Diisopropylethylamine (4.0 mL, 22.9 mmol, 4.0 eq.) was added to a mixture of 28 (2.0 g, 5.23 mmol, 1.0 eq.) and (3-chloro-4-methoxyphenyl)methanamine hydrochloride [29] (1.8 g, 8.41 mmol, 1.6 eq) in n-propanol (40 mL). The resulting mixture was heated at reflux for 16 h. After cooling to room temperature, water (40 mL) was added to the reaction mixture. The formed precipitate was filtered, washed successively with water (20 mL) and ethanol (20 mL) and then dried in a desiccator to afford the desired product 29 (2.3 g, 4.44 mmol, 85%) as a white solid. Rf (SiO2, cyclohexane/ethyl acetate, 7/3, v/v): 0.48; Mp: 140-142 C; IR (cm-1): 1701 (nuC=O), 1320 (nuCF3), 1281 (nuC-O), 1110 (nuC-O), 1031 (nuC-O); 1H NMR (CDCl3, 400 MHz) delta 9.79 (brs, 1H, NH), 9.33 (s, 1H, H2), 8.41 (m, 1H, H5), 8.18 (d, 1H, 4JH7-H5 = 1.5 Hz, H7), 7.40 (d, 1H, 4JH2?-H6?= 2.2 Hz, H2?), 7.24 (m, 1H, H6?), 6.96 (d, 1H, 3JH5?-H6?= 8.5 Hz, H5?), 4.87 (d, 2H, 3JHd-NH = 5.9 Hz, Hd), 4.40 (q, 2H, 3JHb-Hc= 7.1 Hz, Hb), 3.92 (s, 3H, He), 1.41 (t, 3H, 3JHc-Hb= 7.1 Hz, Hc); 13C NMR (CDCl3, 100 MHz) delta 167.3 (Ca), 154.5 (C4), 154.1 (2C, C4?, C8a), 148.6 (C2), 131.1 (C1?), 130.2 (C2?), 129.6 (C6?), 127.9 (C7), 126.2 (C8), 125.2 (q, 2JC6-F = 33 Hz, C6), 123.8 (d, 1JCF3-F = 271 Hz, CF3), 123.4 (C3?), 121.6 (C5), 120.1 (C4a), 113.4 (C5?), 105.9 (C3), 61.5 (Cb), 56.6 (Ce), 49.9 (Cd), 14.4 (Cc); HRMS calculated for C21H1779Br35ClF3N2O3 [M+H]+ m/z 517.0141, found C21H1779Br35ClF3N2O3 [M+H]+ m/z 517.0150 (77%); C21H1781Br35ClF3N2O3 or C21H1779Br37ClF3N2O3 [M+H]+ m/z 519.0163 (100%); C21H1781Br37ClF3N2O3 [M+H]+ m/z 521.0134 (24%).

These compound has a wide range of applications. It is believed that with the continuous development of the source of the synthetic route 3-Chloro-4-methoxybenzylamine Hydrochloride, its application will become more common.

Reference:
Article; Liu, Jianrong; Maisonial-Besset, Aurelie; Wenzel, Barbara; Canitrot, Damien; Baufond, Ariane; Chezal, Jean-Michel; Brust, Peter; Moreau, Emmanuel; European Journal of Medicinal Chemistry; vol. 136; (2017); p. 548 – 560;,
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. 261762-56-5, name is 1-Chloro-2-fluoro-3-methoxybenzene, A new synthetic method of this compound is introduced below., Formula: C7H6ClFO

1 g (6.2 mmol) 3-Chloro-2-fluoroanisole in 20 ml THF was cooled to -70 C. and 2.7 ml of a 2.5 M n-butyl lithium solution in hexane were added. After one hour at -70 3.93 ml DMF in 7 ml THF were added at -70 C. and the mixture is stirred another hour at -70 C. 15 ml of a 1 M aqueous hydrochloric acid were added and the reaction was warmed to ambient temperature over 18 hours. The reaction mixture was partitioned between diethyl ether and water. The aqueous phase was extracted with diethyl ether, the combined organic phases were washed with brine, dried over sodium sulfate and evaporated. The crude product was purified by chromatography on silica gel to yield 0.25 g 2-chloro-3-fluoro-4-methoxybenzaldehyde. 1H-NMR (CDCl3); delta=3.98 (s, 3H), 6.98 (dd, 1H), 7.75 (dd, 1H), 10.30 (s, 1H).

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 SCHERING PHARMA AKTIENGESELLSCHAFT; ASTRAZENECA AB; US2010/16338; (2010); A1;,
Chloride – Wikipedia,
Chlorides – an overview | ScienceDirect Topics

51419-59-1, name is p-Tolylmethanesulfonyl chloride, 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. COA of Formula: C8H9ClO2S

A solution of 1-(4-Amino-phenyl)-3-pyridin-4-ylmethyl-urea (80 mg, 0.33 mmol) in DIVIF (3 mL) was added p-Tolyl-methanesulfonyl chloride (94.7 mg, 0.46 mmol) and TEA (168.4 mg, 1.65 mmol). The reaction mixture was stirred at room temperature overnight. The mixture was washed H20 (10 mL) and extracted with EA (50 mL). The combined organic phase was dried over Na2SO4, filtered and concentrated. The residue was purified by prep-HPLC (5-95; NH4HCO3) to give n- [4-(3 -pyridin-4-ylmethyl-ureido)-phenyl] -c-p-tolyl-methanesulfonamide (35 mg, yield 26percent) as a white solid. ?H NMR (400 IVIHz, DMSO-d6): oe = 9.49 (s, 1H), 8.68 (s, 1H), 8.51-8.49 (m, 2H), 7.37 (d, J 8.8 Hz, 2H), 7.28 (d, J 5.6 Hz, 2H), 7.18-7.13 (m, 4H), 7.08 (d, J= 8.8 Hz, 2H), 6.71 (t, J= 5.6 Hz, 1H), 4.32 (d, J 5.6 Hz, 2H), 4.29 (s, 2H), 2.29 (s, 3H). MS: m/z 410.9 (M+HH).

The synthetic route of 51419-59-1 has been constantly updated, and we look forward to future research findings.

Reference:
Patent; SANFORD BURNHAM PREBYS MEDICAL DISCOVERY INSTITUTE; GARDELL, Stephen; PINKERTON, Anthony B.; SERGIENKO, Eduard; SESSIONS, Hampton; (428 pag.)WO2018/132372; (2018); A1;,
Chloride – Wikipedia,
Chlorides – an overview | ScienceDirect Topics

Reference of 2613-34-5, The chemical industry reduces the impact on the environment during synthesis 2613-34-5, name is 3-Chloro-2,4-difluoroaniline, I believe this compound will play a more active role in future production and life.

3-Chloro-2,4-difluoro-(trifluoroacetamido)benzene. To a solution of 10.5 g (64.3 mmol) of 3-chloro-2,4-difluoroaniline in 25 mL of dioxane kept in an ice-bath was added dropwise 10 mL (14.8 g, 70.4 mmol) of trifluoroacetic anhydride. The solution was stirred at room temperature for 20 h. It was then added to 150 mL of ice-water and the mixture was stirred for 1 h. It was filtered, washed with water, and dried to leave an almost colorless solid 16.1 g (96%); mp 73-74 C.; 1 H NMR (CDCl3), 7.068 (m, 1), 7.976 (mb, 1), 8.146 (m, 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, 3-Chloro-2,4-difluoroaniline, other downstream synthetic routes, hurry up and to see.

Reference:
Patent; State of Oregon, acting by and through the Oregon State Board of Higher Education, acting for and on behalf of the Oregon Health Sciences University and the University of Oregon, Eugene Oregon; Acea Pharmaceuticals, Inc.; The Regents of the University of California; US5631373; (1997); A;,
Chloride – Wikipedia,
Chlorides – an overview | ScienceDirect Topics

Adding a certain compound to certain chemical reactions, such as: 367-22-6, name is 4-Chloro-3-fluoroaniline, 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 367-22-6, category: chlorides-buliding-blocks

Step B: 4-Chloro-5-fluoro-2-iodo-phenylamine Iodine chloride (20.6 ml, 1M solution in DCM, 20.6 mmol) was added dropwise to a solution of 4-chloro-3-fluoroaniline (2 g, 13.7 mmol) in methanol (35 ml) at 0 C. and the reaction mixture was stirred for 1 h at room temperature. Volatiles were removed under reduced pressure, water was added and the mixture was extracted with dichloromethane. The combined organic layers were washed with water, dried with Na2SO4 and evaporated. The remaining residue was purified by chromatography with three consecutive columns (silica gel, heptane/EtOAc 98:2-93:7 and twice heptane/EtOAc 98:2-95:5) to obtain the title compound (2.51 g, 67%) as dark red solid. MS (ESI): 272.1 (M+H)+.

At the same time, in my other blogs, there are other synthetic methods of this type of compound, 4-Chloro-3-fluoroaniline, and friends who are interested can also refer to it.

Reference:
Patent; Hoffmann-La Roche Inc.; Ceccarelli, Simona M.; Conte, Aurelia; Kuehne, Holger; Kuhn, Bernd; Neidhart, Werner; Obst Sander, Ulrike; Rudolph, Markus; US2013/116234; (2013); A1;,
Chloride – Wikipedia,
Chlorides – an overview | ScienceDirect Topics

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 1996-29-8 as follows. Safety of 1-Bromo-4-chloro-2-fluorobenzene

To a solution of 1-bromo-4-chloro-2-fluorobenzene (10.0 g, 47.8 mmol) in dry THF (300 ml.) at -78 C under nitrogen was added LDA (2.0 M solution in THF, 31 ml_, 62.1 mmol) dropwise and the mixture was stirred at -78 C for 15 min. DMF (7.00 g, 95.8 mmol) was added and the mixture was allowed to warm to room temperature. The reaction mixture was quenched with a saturated aqueous NH4CI solution and the mixture was extracted with EtOAc (400 ml. x 3). The combined organic extracts were washed with brine (300 ml_), dried over Na2S04, filtered and concentrated under reduced pressure. The residue was purified by silica gel chromatography (100% Pet. Ether) to give the title compound (4.0 g, 35%) as a white solid, which was used directly in the next step.

According to the analysis of related databases, 1996-29-8, the application of this compound in the production field has become more and more popular.

Reference:
Patent; CTXT PTY LIMITED; MORROW, Benjamin, Joseph; CAMERINO, Michelle, Ang; WALKER, Scott, Raymond; STEVENSON, Graeme, Irvine; STUPPLE, Paul, Anthony; (266 pag.)WO2019/219820; (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. 1939-99-7, name is Phenylmethanesulfonyl chloride, This compound has unique chemical properties. The synthetic route is as follows., name: Phenylmethanesulfonyl chloride

Step 1 : N-re^butyl-1 -phenylmethanesulfonamide To a solution of teri-butylamine (2 g, 27.3 mmol) in dichloromethane (90 mL) was added N,N-diisopropylethylamine (5.7 mL, 32.8 mmol), followed by phenylmethanesulfonyl chloride (6.25 g, 32.8 mmol) and the reaction was stirred at ambient temperature for 16 hours. The reaction was then diluted with dichloromethane, washed with water and brine, dried with MgS04, and purified by silica gel column chromatography (0-50% EtOAc in heptane) to give N-teri-butyl-l-phenyl- methanesulfonamide (4.81 g, 77% yield). 1 H NMR (400 MHz, CDC13) delta 7.51 – 7.44 (m, 2H), 7.41 (dd, J= 4.9, 2.0 Hz, 3H), 4.49 (s, 2H), 4.27 (s, 1H), 1.68 (s, 6H); LCMS (m/z) ES+ 228 [M+l]+.

According to the analysis of related databases, 1939-99-7, the application of this compound in the production field has become more and more popular.

Reference:
Patent; F. HOFFMANN-LA ROCHE AG; FAUBER, Benjamin; RENE, Olivier; WO2013/92941; (2013); A1;,
Chloride – Wikipedia,
Chlorides – an overview | ScienceDirect Topics