Category: 108-37-2

Related Products 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;,
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Synthetic Route 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;,
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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., HPLC of 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;,
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108-37-2, 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 108-37-2 as follows.

General procedure: Na2CO3 (212 mg, 2 mmol), 4-chloronitrobenzene (1 mmol) and styrene (1.5 mmol) were added successively into a dried Schlenk tube under nitrogen. Then the DMA (0.1mL) solution of DADPP (0.002mmol) and [Pd(C3H5)Cl]2 (0.0005mmol), which was reacted at 100C for 10 min prior to use, was added into the mixture. The reaction was performed at 130C. At the end of reaction, the mixture solution was extracted with ethyl acetate (3×5 mL). Combined organic phase was washed with brine (3×5mL) and dried over MgSO4. The dried solution was filtered and purified with silica gel chromatography (petroleum ether 60-90C) to give a corresponding product.

According to the analysis of related databases, 1-Bromo-3-chlorobenzene, the application of this compound in the production field has become more and more popular.

Reference:
Article; Jiang, Zhi-Jie; Wang, Wei; Zhou, Rong; Zhang, Lei; Fu, Hai-Yan; Zheng, Xue-Li; Chen, Hua; Li, Rui-Xiang; Catalysis Communications; vol. 57; (2013); p. 14 – 18;,
Chloride – Wikipedia,
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Reference 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.

General procedure: A 50 mL roundbottom flask wascharged with 0.5 mmol of aryl halide, benzene (4 mL) and1.5 mmol of KO(t-Bu). The flask was fitted with a refluxcondenser left open to air. Then, a solution of catalyst dissolved in 420 muL DMF was added to the reaction. The reactionwas then stirred and refluxed for 40 h. The reaction was workedup by extraction with ether and washed with deionized H2O.The organic phase was collected and dried over anhydrous sodium sulfate. The residue was purified by flash column chromatography. NMR spectra of isolated products matched well withthe literature.

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

Reference:
Article; Tamang, Sem Raj; Hoefelmeyer, James D.; Beilstein Journal of Organic Chemistry; vol. 12; (2016); p. 2757 – 2762;,
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.

A solution of i-butyl piperazine-l-carboxylate (1.96 g, 10.54 mmol, 2.00 equiv), 1- bromo-3-chlorobenzene (1 g, 5.26 mmol, 1.00 equiv), BINAP (330 mg, 0.53 mmol, 0.10 equiv), Pd2(dba)3 (243.8 mg, 0.27 mmol, 0.05 equiv), NaOi-Bu (1.59 g, 16.56 mmol, 3.00 equiv), and toluene (17 mL) was placed in a 100-mL round bottom flask, stirred overnight at 100C in an oil bath, and concentrated under vacuum. Purification via silica gel column (PE/EA (50:1)) yielded 1.3 g (83%) of i-butyl 4- (3-chlorophenyl)piperazine-l-carboxylate as a yellow solid. LC-MS (ES, m/z): 297 [M+H]+

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

Reference:
Patent; BIOENERGENIX; MCCALL, John, M.; MCKEARN, John; ROMERO, Donnal, L.; CLAIR, Michael; WO2011/28947; (2011); A2;,
Chloride – Wikipedia,
Chlorides – an overview | ScienceDirect Topics

Reference 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.

A 1.6 molar solution of butyllithium in hexanes (4.5 mL, 2.8 mmol) was placed in a three-neck flask equipped with a STIRRER, addition funnel, low-temperature thermometer and nitrogen inlet tube at 0 C. A solution of diisopropyl amine (1.13 mL, 8.1 mmol) in anhydrous tetrahydrofuran was added dropwise. The resulting solution was stirred at 0 C for ten minutes, then cooled to-78 C. Upon cooling, a solution of L-BROMO-3- chlorobenzene (1.4 g, 7.3 mmol) in anhydrous tetrahydrofuran was added dropwise. The reaction was allowed to stir at-78 C for one hour. Anhydrous dimethylformamide (636 GEL) was added. The solution was allowed to slowly warm to room temperature, followed by the addition of acetic acid (50 mL) and water (50 mL). The aqueous mixture was extracted with ether twice and the ether layers were separated. The combined ether layers were successively washed with aqueous hydrochloric acid and brine. The separated organic layer was dried over anhydrous sodium sulfate, filtered and concentrated under reduced pressure. The resulting residue was purified by flash column chromatography on silica gel, eluting with 9: 1 hexanes: ethyl acetate to yield 2-chloro-6-bromobenzaldehyde as an off white solid (850 mg, 53 % yield). NMR (300 MHz, CDC13): 10.4 (s, 1H), 7.6 (m, 1H), 7.45 (m, 1H), 7.3 ppm (m, 1H).

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

Reference:
Patent; RIGEL PHARMACEUTICALS, INC.; WO2004/99164; (2004); 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. 108-37-2, name is 1-Bromo-3-chlorobenzene, This compound has unique chemical properties. The synthetic route is as follows., Computed Properties of C6H4BrCl

To a solution of diisopropylamine (76 mL, 0.4 mol) in anhydrous THF (664 mL) and n-hexane (220 mL) was added 2.5 M n-BuLi (160 mL, 0.4 mol) dropwise at -78 C. over 1 h. The mixture was stirred for 1 h at -78 C. and a solution of 1-bromo-3-chlorobenzene (76 g, 0.4 mol) in anhydrous THF (300 mL) was added dropwise at -78 C. 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 C. The temperature was raised from -78 C. to rt 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 1-bromo-3-fluoro-2-iodobenzene (115 g, 91%). 1H NMR (400 MHz, CDCl3) delta ppm 7.12-7.18 (t, 1H), 7.35-7.41 (dd, 1H), 7.49-7.54 (dd, 1H); MS (E/Z): 317 (M+H+)

According to the analysis of related databases, 108-37-2, the application of this compound in the production field has become more and more popular.

Reference:
Patent; Baldwin, John J.; Cacatian, Salvacion; Claremon, David; Dillard, Lawrence W.; Flaherty, Patrick T.; Ghavimi-Alagha, Bahman; Ghirlanda, Damiano; Ishchenko, Alexey V.; Kallander, Lara S.; Lawhorn, Brian; Lu, Qing; McGeehan, Gerard; Knapp-Reid, Beth A.; Semus, Simon; Simpson, Robert D.; Singh, Suresh B.; Terrell, Lamont R.; Tice, Colin; Tran, Tritin; Xu, Zherong; Yuan, Jing; Zhao, Wei; Zhao, Yongdong Y.; US2010/317697; (2010); A1;,
Chloride – Wikipedia,
Chlorides – an overview | ScienceDirect Topics

Related Products 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.

A flask containing (l,5-cyclooctadiene)(methoxy)-iridium(I) dimer (84 mg, 0.13 mmol), 4,4′-di-tert butyl-2-2′-dipyridyl (69 mg, 0.26 mmol) and bis(pinacolato)diboron (1.29 g, 5.11 mmol) was purged with Ar, then hexanes (26 mL) and l-bromo-3- chlorobenzene (1 mL, 8.51 mmol) were added sequentially. The solution was stirred at RT for 18 h. The reaction mixture was concentrated in vacuo, re-dissolved in acetone (26 mL), then oxone (5.23 g, 8.51 mmol) in water (26 mL) added [Caution: exotherm observed]. After 10 min, the reaction mixture was diluted with DCM. The layers separated, and the aqueous layer extracted with DCM. The combined organics were washed with brine, dried and concentrated in vacuo to give the title compound (1.43 g, 81%). LCMS (Method 3): Rt 3.74 min, m/z 205, 207 [M-H+].

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

Reference:
Patent; CHIESI FARMACEUTICI S.P.A.; ALCARAZ, Lilian; HURLEY, Christopher; CRIDLAND, Andrew, Peter; JENNINGS, Andrew, Stephen, Robert; WO2014/195402; (2014); A1;,
Chloride – Wikipedia,
Chlorides – an overview | ScienceDirect Topics

Synthetic Route of 108-37-2, 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. 108-37-2, name is 1-Bromo-3-chlorobenzene, This compound has unique chemical properties. The synthetic route is as follows.

To a solution of diisopropylamine (76 mL, 0.4 mol) in anhydrous THF (664 mL) and n-hexane (220 mL) was added 2.5 M n-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 rt 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 (115 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 chemical industry reduces the impact on the environment during synthesis 1-Bromo-3-chlorobenzene. I believe this compound will play a more active role in future production and life.

Reference:
Patent; SMITHKLINE BEECHAM CORPORATION; VITAE PHARMACEUTICALS, INC.; WO2008/124575; (2008); A1;,
Chloride – Wikipedia,
Chlorides – an overview | ScienceDirect Topics