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Usage

Uses

1. Organic Synthesis:
4'-Bromoacetanilide is used as an intermediate in organic synthesis, playing a crucial role in the formation of various complex organic compounds.
2. Analytical Chemistry (Environmental and Pharmaceutical Applications):
Used in Environmental Analysis:
4'-Bromoacetanilide is employed as an internal standard for the determination of phenylurea and triazine herbicides, as well as their transformation products in oysters. This application aids in the accurate quantification and analysis of these contaminants in the environment.
Used in Pharmaceutical Analysis:
4'-Bromoacetanilide serves as an internal standard for phenylurea and its respective metabolic products, ensuring the precision and reliability of pharmaceutical analysis.
3. Material Science (Coordination Chemistry and Surface Modification):
Used in the Synthesis of New Ligands:
4'-Bromoacetanilide is utilized in the production of a new ligand for the formation of a coordination complex between gadolinium(III) and titanium(IV) oxide (TiO2). This coordination complex has potential applications in various fields, including catalysis and material science.
Used for Surface Modification:
4'-Bromoacetanilide is involved in the synthesis of new ligands for anchoring Gd(III) chelates onto the TiO2 surface, which can enhance the properties of the material for specific applications, such as in solar energy conversion or photocatalysis.

Preparation

Preparation of 4'-Bromoacetanilide from Acetanilide. Principle: Aromatic compounds can be conveniently brominated by the use of brominating agent, which is normally a solution of bromine in acetic acid. Bromination of activated aromatic compounds usually give 2, 4, 6-tribromo derivatives while moderately activating group like anilide give preferably the para bromo product. Reaction: Procedure: Dissolve 0.5 g acetanilide in 0.6 ml glacial acetic acid and add 2.5 ml bromine solution in acetic acid (25% w/v). Shake the mixture for 1 h. After 1 h, pour the mixture on to crushed ice (20 g) with stirring. Filter the separated product and wash with cold water. Dry the product, record the practical yield and re-crystallize it. Re-crystallization: Dissolve the crude product in minimum amount of ethyl alcohol in a beaker by heating on a water bath. Filter the hot solution and cool the filtrate. The crystals of the product separate out. Filter, dry and record the melting point and TLC (using toluene as a solvent).

Synthesis Reference(s)

Canadian Journal of Chemistry, 50, p. 1233, 1972 DOI: 10.1139/v72-193Synthetic Communications, 23, p. 779, 1993 DOI: 10.1080/00397919308009839

Purification Methods

Crystallise the anilide from aqueous MeOH or EtOH. Purify it by zone refining. [Beilstein 12 IV 1504.]

Upstream product

• 56-23-5 tetrachloromethane 
• 77-48-5 1,3-dibromo-5,5-dimethylimidazolidine-2,4-dione 
• 103-84-4 Acetanilid 
• 64-17-5 ethanol 
• 1439-12-9 N-bromo-acetanilide 
• 10341-75-0 (E)-1-phenylethanone oxime 
• 579-11-3 N-chloroacetanilide 
• 95262-09-2 3-[(4-bromophenyl)amino]-3-oxopropanoic acid 
• 139696-89-2 N-(4-(methylsulfinyl)phenyl)acetamide 
• 95196-99-9 N,N’-bis(4-bromophenyl)sulfamide 
• 127-09-3 sodium acetate 
• 108-24-7 acetic anhydride 
• 106-40-1 4-bromo-aniline 
• 64-19-7 acetic acid 

Downstream Products

• 586-78-7 para-nitrophenyl bromide 
• 134835-91-9 1-acetyl-1,3-di-(p-bromophenyl)urea 
• 54818-87-0 N-(4-phenylsulfanyl)phenyl acetamide 
• 98437-33-3 1-(4'-bromophenyl)-5-methyl-1H-tetrazole 
• 35920-23-1 acetic acid-(4-bromo-N-nitroso-anilide) 
• 121-62-0 N-acetylsulfanilic acid 
• 881-50-5 N-(4-bromo-2-nitrophenyl)acetamide 
• 20980-00-1 N-(4-bromophenyl)thioacetamide 
• 1576-59-6 2-amino-5-bromobenzenesulfonic acid 
• 3460-23-9 N-(4-bromo-2-chlorophenyl)acetamide 
• 99233-43-9 4,N-dibromoacetanilide 
• 23373-04-8 2',4'-dibromoacetanilide 
• 62554-90-9 4-bromo-2,6-dinitroaniline 
• 29551-82-4 acetic acid-(4-bromo-N-chloro-anilide) 

Relevant academic research and scientific papers

Ultrasound promoted bromination of activated arenes with N-bromosuccinimide

Ultrasound irradiation has resulted in the selective monobromination of activated aromatics with N-Bromosuccinimide (NBS) in carbon tetrachloride at ambient conditions in the absence of any added catalyst.

Synthesis of Flubromazepam Positional Isomers for Forensic Analysis

Designer benzodiazepines have recently appeared in many forensic cases as legal alternatives to federally scheduled drugs such as diazepam (Valium) and alprazolam (Xanax). Though current forensic instrumental techniques are often sufficient for identifying novel psychoactive substances, they may not readily differentiate between potential positional isomers. Additionally, characterization data for positional isomers of known designer benzodiazepines are widely nonexistent. In this study, flubromazepam, a recognized designer benzodiazepine since 2012, was targeted for synthesis and characterization due to its potential for federal scheduling and current legal status within the United States. A practical synthetic method was developed to prepare purified reference materials for each positional isomer of flubromazepam in which the positions of the bromine and fluorine substituents were varied. Possible isomers (9 of the 12) were successfully prepared and used for further analysis.

Use of 1-halo derivatives of the 2,2,6,6-tetramethylpiperidine series as oxidants and halogenating agents

1-Halo derivatives of the 2,2,6,6-tetramethylpiperidine series oxidize sterically hindered phenols to form dimers and p-quinones.

Bromodecarbonylation and bromodecarboxylation of electron-rich benzaldehydes and benzoic acids with oxone and sodium bromide

Benzaldehydes and benzoic acids bearing ortho- and paraelectron donating substituents having unshared electron-pair have undergone bromodecarbonylation or bromodecarboxylation on treatment with sodium bromide in the presence of Oxone in aqueous methanol.

Selective Oxidative Coupling Reaction of Isocyanides Using Peroxide as Switchable Alkylating and Alkoxylating Reagent

A switchable oxidative coupling reaction of isocyanide and peroxide has been disclosed. In the presence of iron catalyst, the coupling reaction affords N-arylacetamides in good yields. By simply replacing the iron with copper catalyst, another different coupling reaction takes place in which peroxide can serve as alkoxylating source. This protocol represents a new fundamental coupling of two basic chemicals involving C?C and C?O bond-forming process. The unusual reactivity of an isocyano group in a radical reaction acting formally as an amidoyl synthon has also been well established. The experiment outcome reveals that aromatic isocyanides are particularly compatible reaction partners in present coupling reaction, whereas no desired products are observed when aliphatic isocyanides are used. (Figure presented.).

Regioselective and high-yielding bromination of aromatic compounds using hexamethylenetetramine-bromine

A regioselective and highly efficient method for bromination of aromatic compounds in the presence of a stoichiometric amount of hexamethylenetetramine- bromine (HMTAB) as an efficient reagent in dichloromethane is reported. The selectivity depends on the temperature and nature of the substituent on the substrate. The reactivity of this reagent was increased by supporting it to silica gel for bromination of less activated compounds.

Liquid phase regioselective bromination of aromatic compounds over HZSM-5 catalyst

A simple, efficient, regioselective and environmentally safe method for oxybromination of activated aromatics catalyzed by HZSM-5 is reported. The electrophilic substitution of bromine generated from KBr using HZSM-5 as a catalyst and H2O2 as an oxidant.

Environmentally benign indole-catalyzed position-selective halogenation of thioarenes and other aromatics

Halogenated aromatic compounds are the cores of many pharmaceutical, agricultural and chemical products but they are commonly prepared using electrophilic halogenation reactions in non-green chlorinated solvents under harsh conditions. A separate problem happens in the aromatic halogenation of thioarenes because they readily undergo oxidative side-reactions. Herein we report an environmentally benign electrophilic bromination of aromatics using an indole-catalytic protocol, which is suitable for a wide range of substrates including thioarenes.

Selectivity enhancement of aromatic halogenation reactions at the micellar interface: Effect of highly ionic media

Halogenation (iodination and bromination) of various aromatic compounds has been studied in micellar media in order to observe the effect on regioselectivity and conversion of the reaction. The addition of surfactant causes a change in the chemical shifts of the aromatic proton resonance of phenol which proves the orientation of the aromatic compound on the micellar surface. However, increase in ionic strength of the reaction media affects the selectivity of reaction by disturbing this spatial orientation of the aromatic compound in the micelle. Selectivity towards particular isomers is dependent on the concentration of the surfactant. In bromination of chlorobenzene (deactivated aromatic compound) enhancement in selectivity and conversion towards the para isomer has been observed.

A new mild and selective reagent for nuclear bromination

Hexamethylene tetramine tribromide HMTAHBr3 - a new, mild and regioselective brominant is reported for bromination of aromatic hydrocarbons, substituted ethers, phenols and anilides in high yields.