5344-78-5

Usage

Uses

1. Used in Pharmaceutical Industry:
4-Bromo-3-nitroanisole is used as a synthetic intermediate for the production of various pharmaceutical compounds. Its application reason is due to its ability to be transformed into different molecules with potential therapeutic properties.
2. Used in Chemical Synthesis:
4-Bromo-3-nitroanisole is used as a key building block in the synthesis of various organic compounds, such as:
a) 4-bromo-5-methoxyaniline: 4-Bromo-3-nitroanisole is used in the production of dyes and pigments, as well as in the pharmaceutical industry for the synthesis of drugs with potential therapeutic applications.
b) 2-(4-methoxy-2-nitrophenylsulfanyl)benzoic acid: 4-Bromo-3-nitroanisole has potential applications in the development of new materials and chemicals with specific properties.
c) 4-(1-diethylamino-4-pentylamino)-3-nitrochlorobenzene: 4-Bromo-3-nitroanisole can be used in the synthesis of advanced organic materials and may have potential applications in various industries, including electronics and pharmaceuticals.

InChI:InChI=1/C7H6BrNO3/c1-12-5-2-3-6(8)7(4-5)9(10)11/h2-4H,1H3

Upstream product

• 33844-21-2 2-nitro-4-methoxybenzoic acid 
• 59557-92-5 2-bromo-5-methoxyaniline 
• 104-92-7 1-bromo-4-methoxy-benzene 
• 51-66-1 4-methoxyacetanilide 
• 119-81-3 4-methoxy-2-nitroacetanilide 
• 96-96-8 4-methoxy-2-nitroaniline 
• 577-72-0 4-methoxy-3-nitroaniline 

Downstream Products

• 168209-84-5 4-methoxy-2-nitro-N-propylaniline 
• 92906-29-1 N-(2-nitro-4-methoxyphenyl)anthranilic acid 
• 66910-63-2 N⁴,N⁴-diethyl-N¹-(4-methoxy-2-nitro-phenyl)-1-methyl-butanediyldiamine 
• 581-46-4 3,3'-bipyridine 
• 75753-19-4 4,4'-dimethoxy-2,2'-dinitrobiphenyl 
• 4373-75-5 3-(4-methoxy-2-nitrophenyl)-pyridine 
• 3189-13-7 6-methoxylindole 
• 126759-34-0 1-methoxy-3-nitro-4-vinylbenzene 
• 77896-32-3 2,4'-dimethoxy-2'-nitrodiphenyl ether 
• 84594-95-6 5-methoxy-1-nitro-2-phenoxybenzene 
• 181995-78-8 1-(4-methoxy-2-nitrophenyl)pyrrolidine 
• 78137-76-5 4-bromo-3-nitrophenol 
• 16098-16-1 4-methoxy-2-nitro-1,1'-biphenyl 
• 81224-16-0 7-bromo-4-methoxy-1H-indole 

Relevant academic research and scientific papers

The polyhedral nature of selenium-catalysed reactions: Se(iv) species instead of Se(vi) species make the difference in the on water selenium-mediated oxidation of arylamines

Selenium-catalysed oxidations are highly sought after in organic synthesis and biology. Herein, we report our studies on the on water selenium mediated oxidation of anilines. In the presence of diphenyl diselenide or benzeneseleninic acid, anilines react with hydrogen peroxide, providing direct and selective access to nitroarenes. On the other hand, the use of selenium dioxide or sodium selenite leads to azoxyarenes. Careful mechanistic analysis and 77Se NMR studies revealed that only Se(iv) species, such as benzeneperoxyseleninic acid, are the active oxidants involved in the catalytic cycle operating in water and leading to nitroarenes. While other selenium-catalysed oxidations occurring in organic solvents have been recently demonstrated to proceed through Se(vi) key intermediates, the on water oxidation of anilines to nitroarenes does not. These findings shed new light on the multifaceted nature of organoselenium-catalysed transformations and open new directions to exploit selenium-based catalysis.

Synthesis of 5,9-Diaza[5]helicenes

A new method for the synthesis of 5,9-diaza[5]helicenes is presented using 2,3-bis(acylamino)-substituted ortho-terphenyls as precursors. Activation of the amide groups and electrophilic substitution at the ortho positions of the adjacent phenyl groups leads to the 5,9-diaza[5]helicenes. A stepwise reaction including protection of the first amino group, amide formation at the second amino group with subsequent cyclization, followed by deprotection, amide formation and cyclization at the first amino group ensures that both electrophilic substitutions take place at sufficiently activated arenes and allows for the different substituents at the diaza[5]helicenes brought in with the amide groups. The terphenyl precursors are synthesized by two Suzuki couplings of suitably substituted building blocks. Three different 5,9-diaza[5]helicenes with aliphatic, alkenyl and methoxycarbonylalkyl substituents were prepared; the latter would allow to attach further functionalities by ester or amide linkage.

Inexpensive NaX (X = I, Br, Cl) as a halogen donor in the practical Ag/Cu-mediated decarboxylative halogenation of aryl carboxylic acids under aerobic conditions

Versatile and practical Ag/Cu-mediated decarboxylative halogenation between readily available aryl carboxylic acids and abundant NaX (X = I, Br, Cl) has been achieved under aerobic conditions in moderate to good yields. The halodecarboxylation is shown to be an effective strategy for S-containing heteroaromatic carboxylic acid and benzoic acids with nitro, chloro and methoxyl substituents at the ortho position. A gram-scale reaction and a three-step procedure to synthesize iniparib have been performed to evaluate the practicality of this protocol. A preliminary mechanistic investigation indicates that Cu plays a vital role and a radical pathway is involved in the transformation.

PROCESS FOR THE PREPARATION OF ORGANIC HALIDES

The present invention provides a halo-de-carboxylation process for the preparation of organic chlorides, organic bromides and mixtures thereof, from their corresponding carboxylic acids, using a chlorinating agent selected from trichloroisocyanuric acid (TCCA), dichloroisocyanuric acid (DCCA), or combination thereof, and a brominating agent.

Synthetic method of aryl halide taking aryl carboxylic acid as raw material

A synthetic method of an aryl halide taking aryl carboxylic acid as a raw material is characterized in that a corresponding aryl halide is formed by carrying out substitution reaction on an aryl carboxylic acid compound and haloid salt MX in an organic solvent under the condition that oxygen, a silver catalyst, a copper additive and a bidentate nitrogen ligand exist, wherein M in MX represents alkali metal or alkaline earth metal, and X represents F, Cl, Br or I. Compared with a conventional aryl halide synthetic method, the synthetic method disclosed by the invention has the obvious advantages that reaction raw materials (comprising aryl carboxylic acid and MX) are cheap and easy to obtain, the using amount of a metal catalyst is small, pollution to the environment when the oxygen is used as an oxidant is the smallest, good tolerance to various functional groups on an aromatic ring is obtained, the yield is high, and the like. The synthetic method disclosed by the invention can be widely applied to synthesis in the fields of medicine, materials, natural products and the like in industry and academia.

Decarboxylative Halogenation and Cyanation of Electron-Deficient Aryl Carboxylic Acids via Cu Mediator as Well as Electron-Rich Ones through Pd Catalyst under Aerobic Conditions

Simple strategies for decarboxylative functionalizations of electron-deficient benzoic acids via using Cu(I) as promoter and electron-rich ones by employing Pd(II) as catalyst under aerobic conditions have been established, which lead to smooth synthesis of aryl halides (-I, Br, and Cl) through the decarboxylative functionalization of benzoic acids with readily available halogen sources CuX (X = I, Br, Cl), and easy preparation of benzonitriles from decarboxylative cyanation of aryl carboxylic acids with nontoxic and low-cost K4Fe(CN)6 under an oxygen atmosphere for the first time.

Halogenation and DNA cleavage via thermally stable arenediazonium camphorsulfonate salts

A series of stable arenediazonium camphorsulfonate salts (2a-2j) were synthesized by simple diazotization of several aromatic amines in the presence of sodium nitrite and camphorsulfonic acid. All the new arenediazonium camphorsulfonates, which were characterized by multinuclear (1H and 13C) NMR, IR, DSC, and X-ray diffraction analysis (2e and 2f) provide unambiguous proof for the molecular structures of 2e and 2f. The efficient application of these salts in halogenation reactions was studied in solvent and solvent-free conditions and the DNA cleavage activity was also assessed. These arenediazonium camphorsulfonate salts are noticed as efficient DNA cleaving agents.

Aromatic nitration with bismuth nitrate in ionic liquids and in molecular solvents: A comparative study of Bi(NO3)3·5H 2O/[bmim][PF6] and Bi(NO3)3· 5H2O/1,2-DCE systems

A suspension of bismuth nitrate pentahydrate (BN) in [bmim][PF6] or [bmim][BF4] imidazolium ionic liquid (IL) is an effective reagent for ring nitration of activated aromatics under mild conditions without the need for external promoters. Nitration can also be effected in 1,2-DCE, MeCN, or MeNO2 without additives. Nitration of activated arenes (anisole, toluene, ethylbenzene, cumene, p-xylene, mesitylene, durene, and 1,3-dimethoxybenzene) is considerably faster (time to completion) in BN/[bmim][PF6] relative to BN/1,2-DCE and there are also differences in isomer distributions (for anisole, toluene, and ethylbenzene). With introduction of strongly deactivating substituents (-CHO; -MeCO; -NO 2) the BN/IL system is no longer active but reactions still proceed with BN/1,2-DCE in reasonable yields. The ready availability and low cost of BN, simple operation, and absence of promoters, coupled to recycling and reuse of the IL, provide an attractive alternative to classical nitration methods for activated arenes. Switching from Bi(NO3)3·5H 2O/[bmim][PF6] to Bi(NO3)3· 5H2O/1,2-DCE increases the scope of the substrates that can be nitrated.

Ex situ generation of stoichiometric and substoichiometric 12CO and 13CO and its efficient incorporation in palladium catalyzed aminocarbonylations

A new technique for the ex situ generation of carbon monoxide (CO) and its efficient incorporation in palladium catalyzed carbonylation reactions was achieved using a simple sealed two-chamber system. The ex situ generation of CO was derived by a palladium catalyzed decarbonylation of tertiary acid chlorides using a catalyst originating from Pd(dba)2 and P(tBu)3. Preliminary studies using pivaloyl chloride as the CO-precursor provided an alternative approach for the aminocarbonylation of 2-pyridyl tosylate derivatives using only 1.5 equiv of CO. Further design of the acid chloride CO-precursor led to the development of a new solid, stable, and easy to handle source of CO for chemical transformations. The synthesis of this CO-precursor also provided an entry point for the late installment of an isotopically carbon-labeled acid chloride for the subsequent release of gaseous [ 13C]CO. In combination with studies aimed toward application of CO as the limiting reagent, this method provided highly efficient palladium catalyzed aminocarbonylations with CO-incorporations up to 96%. The ex situ generated CO and the two-chamber system were tested in the synthesis of several compounds of pharmaceutical interest and all of them were labeled as their [ 13C]carbonyl counterparts in good to excellent yields based on limiting CO. Finally, palladium catalyzed decarbonylation at room temperature also allowed for a successful double carbonylation. This new protocol provides a facile and clean source of gaseous CO, which is safely handled and stored. Furthermore, since the CO is generated ex situ, excellent functional group tolerance is secured in the carbonylation chamber. Finally, CO is only generated and released in minute amounts, hence, eliminating the need for specialized equipment such as CO-detectors and equipment for running high pressure reactions.

Selective activation of enantiotopic C(sp3)-hydrogen by means of chiral phosphoric acid: Asymmetric synthesis of tetrahydroquinoline derivatives

Chiral phosphoric acid-catalyzed asymmetric C-H functionalization has been achieved. In this process, enantiotopic C(sp3)-hydrogen is selectively activated by chiral phosphoric acid to afford tetrahydroquinoline derivatives with excellent enantioselectivities (up to 97% ee).