Category: 108-37-2

108-37-2, name is 1-Bromo-3-chlorobenzene, 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. Recommanded Product: 108-37-2

General procedure: The substituted aryl bromide (1.0 mmol), 8-hydroxyquinoline (20 mol%) and KOtBu (2.0 mmol) were loaded into a Schlenk tube equipped with a Teflon-coated magnetic stir bar. The unactivated arene (8.0 mL or 80 equiv) was then added and the mixture was stirred at r.t. for 3-5 min. The Schlenk tube was placed in a preheated oil bath at 80 C and the mixture was stirred for 18 h. After completion of the reaction as judged by GC analysis, the Schlenk tube was allowed to cool to r.t. and the contents quenched with H2O and diluted with EtOAc. The organic layer was separated, and the aqueous layer was extracted with EtOAc. The combined organic layer was dried over Na2SO4 and concentrated under reduced pressure. The crude residue was purified by flash column chromatography on silica gel to afford the desired biaryl product.

The synthetic route of 108-37-2 has been constantly updated, and we look forward to future research findings.

Reference:
Article; Zheng, Xuehua; Wu, Xu-Nian; Chen, Jing-Yi; Luo, Hai-Bin; Wu, Deyan; Wu, Yinuo; Synthesis; vol. 50; 8; (2018); p. 1721 – 1727;,
Chloride – Wikipedia,
Chlorides – an overview | ScienceDirect Topics

Adding a certain compound to certain chemical reactions, such as: 108-37-2, name is 1-Bromo-3-chlorobenzene, 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 108-37-2, Application In Synthesis of 1-Bromo-3-chlorobenzene

A mixture of 3-bromo-l-chlorobenzene (191 mg, 1.0 mmol), 2,5- diazabicyclo [2.2.1]heptane-2-carboxylic acid tert-butyl ester (240 mg, 1.2 mmol), sodium tert-butoxide (135 mg, 1.4 mmol), Pd2 (dba)3 mg, 0.03 mmol), and BINAP (56 mg, 0.09 mmol) in toluene (3 mL) was heated to 110 C for 15 h. After cooling to room temperature, the mixture was filtered through celite, and the filter cake was rinsed with ethyl acetate. The solvents were removed in vacuo. Column chromatography on silica (hexanes: ethyl acetate 4: 1) of the residue afforded 5-(3-chlorophenyl)-2,5- diazabicyclo [2.2.1]heptane-2-carboxylic acid tert-butyl ester (240 mg, 78% yield) as a yellow solid. ¹H NMR (400 MHz, CDC13, mixture of rotamers) 8 7.10 (q, 1H), 6.65 (d, 1H), 6.50 (m, 1H), 6.40 (d, 1H), 4.62 (s, 0.5H), 4.48 (s, 0.5H), 3.53 (m, 1H), 3.47-3.67 (m, 2H), 3.20-3.08 (dd, 1H), 1.98-1.91 (m, 2H), 1.45 (s, 4.5H), 1.41 (s,

At the same time, in my other blogs, there are other synthetic methods of this type of compound, 1-Bromo-3-chlorobenzene, and friends who are interested can also refer to it.

Reference:
Patent; EXELIXIS, INC.; WO2005/117909; (2005); A2;,
Chloride – Wikipedia,
Chlorides – an overview | ScienceDirect Topics

Application of 108-37-2, A common heterocyclic compound, 108-37-2, name is 1-Bromo-3-chlorobenzene, molecular formula is C6H4BrCl, 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.

This example illustrates the tandem Ir-catalyzed borylation and catalytic amination process. [0064] 3-Aminoboronic acids and esters as shown below are of interest as evidenced by the large number of derivatives synthesized, and by several patents, which note their activity as O-lactamase inhibitors (See, for example, Shoichet et al., WO0035905). Few in number, however, are 1, 3, 5-aminoboronic acids and esters (about 25 compounds by SCIFINDER SCHOLAR). Such substrates may prove useful for further derivatization as they can possess three unique sites for diversity. Furthermore, these compounds may prove ideal as scaffolds for combinatorial libraries. The boronic acid or ester can be transformed into a myriad of functionalities including aryl or vinyl via the Suzuki-Miyuara coupling (Miyaura and Suzuki, Chem. Rev. 95: 2457-2483 (1995); Suzuki, J. Organomet. Chem. 576: 147-168 (1999); Miyaura, In Advances in Metal-Organic Chemistry: Liebeskind, Ed.: JAI: London,; Vol. 6, pp. 187-243 (1998)). If R is a halogen, then there exists a multitude of coupling opportunities (See, for examples, Metal-catalyzed Cross-coupling Reactions; Diederich and Stang, eds.: Wiley: Wienheim, 1998). [0066] Recently, a catalytic aromatic C-H activation/borylation reaction utilizing Ir- or Rh-catalysts was developed. The process is high yielding, functional group tolerant (alkyl, halo, carboxy, alkoxy, and protected amino), chemoselective (1,3-substited arenes give only the 5-boryl product), and efficient (Iverson and Smith, J. Am. Chem. Soc. 121: 7696-7697 (1999); Cho et al., J. Am. Chem. Soc. 122: 12868-12869 (2000); Tse et al., Org. Lett. 3: 2831 (2001); Chao et al., Science 295: 305-308 (2002)). Furthermore, the process allows for the direct construction of aryl boronic esters from hydrocarbon feedstocks without going through an aryl halide. Scheme 2 depicts a prototypical borylation reaction: borylation of benzene using (Ind)Ir(COD)(2 mol %), dppe (2 mol %). The borane of choice is pinacolborane (HBPin). A variety of Ir(I) catalysts can be used, including [Ir(COD)Cl]2, Ir(Indenyl)(C2H4)2, Ir(Indenyl)dppe, and (Indenyl)Ir(COD), in the presence of 2 mol equivalents of PMe3 or 1 mol equivalent of a bidentate ligand like dmpe or dppe. The catalyst system of choice is (Indenyl)Ir(COD), dppe or dmpe (2 mol % each) because of it’s cleanness of reaction and efficient TOF (24 h-1 with benzene). The reaction can be run in the neat arene or in inert solvents (e.g. cyclohexane). During our studies into tandem borylation/Suzuki coupling, we noted difficulties with the hydrolysis of the boronic ester functionality (Bpin). The robustness of the BPin group suggested that, perhaps, the pinacol might serve as a protecting group for the boron. Thus, it was deemed of interest to explore other catalytic transformations in the presence of the BPin group. One such transformation is the Buchwald-Hartwig amination of aryl halides (See, for example; Wolfe et al.,. J. Org. Chem. 65: 1158 (2000); Hartwig et al., J. Org. Chem. 64: 5575 (1999); Wolfe and Buchwald, Angew. Chem. Int. Ed. 38: 2413 (1999)). Initially, the reaction was attempted on pure 1-chloro-3-methylphenyl-5-BPin. As shown in Scheme 3 (Buchwald-Hartwig coupling of 1-chloro-3-methylphenyl-5-BPin with aniline), application of Buchwalds protocol proceeded cleanly to give the desired cross-coupling product in 64.7% and 63.8% yield. The use of PtBu3 improved the yield to 78.8%. Unfortunately, initial attempts to perform the reaction in the ?one-pot? protocol were unsuccessful. Table 1 summarizes the results. In all cases where K3PO4.nH2O was used, a significant amount of pinacol was observed by GC-FID (Entries 1-5). While this is indicative of reaction of the BPin group and is most likely a by-product of Suzuki coupling (in this case, dimerization or oligiomerization of the starting material), no dimers or oligiomers were isolated. Noteworthy, is the formation of the desired product, albeit in low yield (10% GC-FID ratio), using K3PO4.nH2O and PtBu3 when all other attempts using the base failed. With anhydrous K3PO4, results were better (Entries 6-9). Most importantly, no pinacol was formed in these reactions. Changing the base or increasing catalyst loading did not improve the results. The use of PtBu3 led to the best results and after 4 days at 100 C., 34.4% of the desired product was isolated (Entry 10). This result, however, falls short of the reaction performed on pure material and shows that the by-products from the Ir-catalyzed borylation are not completely innocuous. As was previously mentioned, a potential source of concern is the presence of free bidentate phosphines after the borylation, which may interfere with subsequent reactions. In the tandem Suzuki reactions, an aryl chloride was successfully coupled only when dmpe was used as the Ir ligand. Thus, the tandem borylation/Buchwald-Hartwig amination reaction of the present invention was attempted using the (Ind)Ir(COD)/dmpe precatalyst….

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; Board of Trustees of Michigan State University; US2004/24237; (2004); A1;,
Chloride – Wikipedia,
Chlorides – an overview | ScienceDirect Topics

Related Products of 108-37-2, These common heterocyclic compound, 108-37-2, name is 1-Bromo-3-chlorobenzene, 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 solution of diisopropylamine (76 mL, 0.4 mol) in anhydrous THF (664 niL) and n-hexane (220 mL) was added 2.5 M «-BuLi (160 mL, 0.4 mol) dropwise* at -78 0C over 1 h. The mixture was stirred for 1 h at -78 0C and a solution of 1 – bromo-3-chlorobenzene (76 g, 0.4 mol) in anhydrous THF (300 mL) was added dropwise at -78 0C. After stirring for an additional 1 h at the same temperature, a solution of iodine (101 g, 0.4 mol) in anhydrous THF (400 mL) was added dropwise at -78 0C. The temperature was raised from -78 0C to room temperature during 2 h. After stirring for 18 h at rt, the mixture was concentrated in vacuo to give the crude product (120 g) which was distilled under reduced pressure to give l -bromo-3- fluoro-2-iodobenzene (1 15 g, 91%). 1H NMR (400MHz, CDCl3): 7.12-7.18 (t, IH), 7.35-7.41 (dd, IH), 7.49-7.54 (dd, IH); MS (E/Z): 317 (M+H+)

The synthetic route of 108-37-2 has been constantly updated, and we look forward to future research findings.

Reference:
Patent; VITAE PHARMACEUTICALS, INC.; WO2007/117560; (2007); A2;,
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. 108-37-2, name is 1-Bromo-3-chlorobenzene, A new synthetic method of this compound is introduced below., Formula: C6H4BrCl

General procedure: General procedure: a 50 mL ask equipped with a magnetic stir bar was charged with aryboronic acid (1 mmol, 1 equiv), aromatic halides (1.2 mmol, 1.2 equiv), catalyst (2 mol%), base (2 mmol, 2 equiv), DMF (5 mL) solution under CO (1 atm) atmosphere, along with sealed the reaction flask by a rubber stopper and CO was injected into it with a stainless steel gas flowmeter. The mixture was then stirred at 120 C forthe indicated time (SI, Fig. S1). After being allowed to cool to roomtemperature, the reaction mixture was diluted with 5 mL water and extracted with diethyl ether (3 × 5 mL). The organic phases werecombined, and the volatile components were evaporated in a rotaryevaporator. The residue was puried by column chromatography onsilica gel.

The synthetic route of 108-37-2 has been constantly updated, and we look forward to future research findings.

Reference:
Article; Wang, Zheng-Jun; Wang, Xue-Yan; Wang, Xia; Liang, Zhi-Wu; Xu, Xinhua; Catalysis Communications; vol. 101; (2017); p. 10 – 14;,
Chloride – Wikipedia,
Chlorides – an overview | ScienceDirect Topics

Some common heterocyclic compound, 108-37-2, name is 1-Bromo-3-chlorobenzene, molecular formula is C6H4BrCl, 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. name: 1-Bromo-3-chlorobenzene

General procedure: Aryl-halide (0.2 mmol, 1 equiv.), Ir(dtbbpy)(ppy)2PF6 (1.8 mg, 0.002 mmol, 1 mol %), NiI2 (3.1 mg, 0.01mmol, 5 mol %), DMSO (2.0 mL) was added to a 10 mL schlenk flask equipped with a magnetic stirrerbar. This resulting mixture was sealed and degassed via vacuum evacuation and subsequent backfill with ethylene for three times. Then, N,N,N?,N?-tetramethylethylenediamine, TMEDA (60 muL, 2 equiv.)and N,N-diisopropylethylamine, DIPEA (70 muL, 2 equiv.) were subsequently added in this order. The solution was gently bubbled with ethylene balloon for approximately 30 seconds. The solution was then taken up into a 8 mL stainless steel syringe pre-purged with argon, and quickly assembled onto thestop-flow micro tubing, SFMT setup. Solution was pumped into the SFMT at 400 muL/min while maintaining approximately 1:1 gas-liquid slug flow at 250 PSI. Filled SFMT was then irradiated with blueLED (2 meter strip, 18 W) in a 100oC oil bath for 24 hours. The SFMT was wash with DCM (8 mL) and subjected to GC analysis (Figure S5). Then water (30 mL) was added to reaction mixture and extracted with DCM (10 mL) three times. Combined organic layer was successively wash with brine three timesand dried over Na2SO4 and concentrated under reduced pressure. The residue was then subjected to flash column chromatography to yield the product as a mixture of meso/dl isomers (which could not be separated by column chromatography).

These compound has a wide range of applications. It is believed that with the continuous development of the source of the synthetic route 108-37-2, its application will become more common.

Reference:
Article; Li, Jiesheng; Luo, Yixin; Cheo, Han Wen; Lan, Yu; Wu, Jie; Chem; vol. 5; 1; (2019); p. 192 – 203;,
Chloride – Wikipedia,
Chlorides – an overview | ScienceDirect Topics

Application of 108-37-2,Some common heterocyclic compound, 108-37-2, name is 1-Bromo-3-chlorobenzene, molecular formula is C6H4BrCl, 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.

Preparation of 2-bromo-6-chlorobenzaldehyde (i-5b). To a solution of l-bromo-3-chlorobenzene (i-5a) (5 g, 26. mmol) in THF (50 mL) was added LDA (1 M, 31.3 mL, 8.7 mmol) dropwise via an addition funnel at -70 C. The mixture was stirred at -70 C for 1 h. DMF (2.87 mL, 39.1 mmol, 227 mmol) in THF (20 mL) was added dropwise maintaining the internal temperature below -70 C. The reaction was stirred vigorously at -70 C for 1 h. Warmed to -30 C, the reaction was poured into 1 M HCl (100 mL) partitioned between water (10 mL) and DCM (30 mL). The aqueous layer was extracted with DCM (20 mL x 3). The combined organic layers were dried over anhydrous Na2S04 and concentrated in vacuo to afford the title compound (3.6 g, yield: 59 %). LCMS (ESI) calc’d for C7H4BrC10 [M+H]+: 219, found: 219.

The synthetic route of 108-37-2 has been constantly updated, and we look forward to future research findings.

Reference:
Patent; MERCK SHARP & DOHME CORP.; BARR, Kenneth Jay; BEINSTOCK, Corey; MACLEAN, John; ZHANG, Hongjun; BERESIS, Richard Thomas; WO2014/28591; (2014); A2;,
Chloride – Wikipedia,
Chlorides – an overview | ScienceDirect Topics

Application of 108-37-2,Some common heterocyclic compound, 108-37-2, name is 1-Bromo-3-chlorobenzene, molecular formula is C6H4BrCl, 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.

Under similar experimental conditions and reagent amounts in 2.2., the mixture was dissolved in 0.02 mL of IL and 1 mL of DMF. The organic phase was passed through silica gel in order to retain the IL and analyzed by GC and the isolated products characterized by 1H NMR, GC-MS, IR, and mp.

These compound has a wide range of applications. It is believed that with the continuous development of the source of the synthetic route 1-Bromo-3-chlorobenzene, its application will become more common.

Reference:
Article; Cardenas, Juan C.; Fadini, Luca; Sierra, Cesar A.; Tetrahedron Letters; vol. 51; 52; (2010); p. 6867 – 6870;,
Chloride – Wikipedia,
Chlorides – an overview | ScienceDirect Topics

Application of 108-37-2,Some common heterocyclic compound, 108-37-2, name is 1-Bromo-3-chlorobenzene, molecular formula is C6H4BrCl, 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.

The thermal characteristics of this reaction were studied using an HEL Simular reaction calorimeter. The calorimeter was equipped with a double-jacketed, 0.8-liter, glass reactor (6 bars). The inner jacket contained a heat-transfer fluid and the outer jacket was evacuated to insulate the system. A quantity of 26.5 g (0.139 moles, 1 equivalent) of 3-bromochlorobenzene (10), 200 ml of 2-methyltetrahydrofuran (Me-THF) and 15.0 g (0.158 moles, 1.1 equivalents) of anhydrous magnesium chloride was charged to this reactor. The slurry was then cooled to -78 C. A quantity of 91.2 ml (0.158 moles, 1.3 equivalents) of lithium diisopropylamide (LDA, 2M in heptane/THF) was charged into the batch, keeping the temp ?75 C. The batch was held for an hour after LDA addition. A quantity of 15.0 ml (0.194 moles, 1.4 equivalents) of N,N-dimethylformamide was charged into the batch at -78 C., keeping the temperature ?75 C. The mixture was stirred for an hour and gradually warmed to 0 C. At 0 C., the reaction was quenched with 150 ml of 0.5M citric acid solution. The layers were separated and the organic layer was collected and concentrated to dryness. The desired product (12) was isolated in 80% yield and 99% purity by GC.

These compound has a wide range of applications. It is believed that with the continuous development of the source of the synthetic route 1-Bromo-3-chlorobenzene, its application will become more common.

Reference:
Patent; Ji, Yaohui; Rawalpally, Thimma; US2009/118546; (2009); A1;,
Chloride – Wikipedia,
Chlorides – an overview | ScienceDirect Topics

Application of 108-37-2,Some common heterocyclic compound, 108-37-2, name is 1-Bromo-3-chlorobenzene, molecular formula is C6H4BrCl, 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 stirred solution of 3-Bromochlorobenzene (0.50 g, 2.61 mmol) and 1- Cyclopentyl-2-propen-1-ol (1.5 eq, 0.49 g, 3. 88 mmol) in anhydrous N-methylpyrrolidinone (3.0 mL), under argon at room temperature, was added sodium bicarbonate (1.2 eq, 0.26 g, 3.10 mmol) followed by dichlorobis (triphenylphosphine) palladium (II) (0.02 eq, 36. 7 mg, 0.05 mmol). The resulting mixture was heated to 140 C in an oil bath and maintained for 4 hours. The resulting reaction mixture was cooled to room temperature and poured into water (50 mL), and extracted with EtOAc (2 X 25 mL). The organics were washed with water (50 mL) and brine (50 mL) then dried over Na2S04, filtered and concentrated. The crude residue was purified by flash chromatography (1% through 10% EtOAc in Hexanes) to yield the intermediate ketone as a slightly yellow oil (0.49 g, 79%). 1H NMR (CDCl3) : 81. 45-1.87 (m, 8H), 2.70-2. 95 (m, 5H), 7.07 (d, J= 7.0 Hz, 1H), 7.10-7. 25 (m, 3H).

These compound has a wide range of applications. It is believed that with the continuous development of the source of the synthetic route 1-Bromo-3-chlorobenzene, its application will become more common.

Reference:
Patent; PFIZER INC.; WO2003/95441; (2003); A1;,
Chloride – Wikipedia,
Chlorides – an overview | ScienceDirect Topics