106-38-7

Basic information

• Product Name: Benzene,1-bromo-4-methyl-
• Synonyms: Toluene,p-bromo- (8CI);1-Bromo-4-methylbenzene;1-Methyl-4-bromobenzene;4-Bromo-1-methylbenzene;4-Methyl-1-bromobenzene;4-Methylbromobenzene;4-Methylphenyl bromide;4-Tolyl bromide;NSC 6531;p-Bromo(methyl)benzene;p-Bromotoluene;p-Methylbromobenzene;p-Methylphenyl bromide;p-Tolyl bromide;4-Bromotoluene
• CAS NO: 106-38-7
• Molecular Formula: C₇H₇Br
• Molecular Weight: 171.0345
• EINECS: 203-391-8
• Product Categories: alkyl bromide;Building Blocks;Chemical Synthesis;Halogenated Hydrocarbons;Organic Building Blocks;Intermediates;Aromatic Hydrocarbons (substituted) & Derivatives;Organics;Miscellaneous;4-Alkylbromobenzenes (Building Blocks for Liquid Crystals);Building Blocks for Liquid Crystals;Functional Materials;Aryl;C7;Halogenated Hydrocarbons
• Mol File: 106-38-7.mol
• Article Data: 185

Chemical Properties

• Melting Point: 26-29℃
• Boiling Point: 183.8 °C at 760 mmHg
• Flash Point: 69 °C
• Appearance: colourless or pale yellow liquid
• Density: 1.39 g/cm³
• Vapor Pressure: 1.04mmHg at 25°C
• Refractive Index: 1.548
• Storage Temp.: Store below +30°C.
• Solubility: 0.11g/l insoluble
• Water Solubility: <0.1 g/100 mL at 24℃
• Merck: 14,1439
• BRN: 1903636
• CAS DataBase Reference: Benzene,1-bromo-4-methyl-(CAS DataBase Reference)
• NIST Chemistry Reference: Benzene,1-bromo-4-methyl-(106-38-7)
• EPA Substance Registry System: Benzene,1-bromo-4-methyl-(106-38-7)

Safety Data

• Hazard Codes: Xn:Harmful
• Statements: R22:; R36/37/38:
• Safety Statements: S26:; S37/39:
• RIDADR: UN 3077 9/PG 3
• WGK Germany: 3
• RTECS: XS7965600
• TSCA: Yes
• HazardClass: 9
• PackingGroup: III
• Hazardous Substances Data: 106-38-7(Hazardous Substances Data)

Usage

Description

4-Bromotoluene is a p-substituted aryl bromide. As a toluene derivative, it is used as a solvent and starting material for organic synthesis and is found in paints, paint thinners, glues, and other products. 4-Bromotoluene was used in the synthesis of ketones by Cu/Pd-catalyzed decarboxylative cross-coupling reaction. It is also used in manufacturing pharmaceuticals (especially for antihypertensive like losartan, Irbesartan), pesticides and other organic compounds1-3.

References

https://www.sigmaaldrich.com/catalog/search?term=4-Bromotoluene&interface=All&N=0&mode=match%20partialmax&lang=en®ion=US&focus=product https://bbzfrankie.wordpress.com/2013/11/21/application-of-4-bromotoluene/ https://toxnet.nlm.nih.gov/cgi-bin/sis/search/a?dbs+hsdb:@term+@DOCNO+6015

Chemical Properties

white crystalline low melting mass, soluble in ethanol, ether and benzene, insoluble in water. toxic, harmful if swallowed, irritating to eyes, respiratory system and skin. 4-bromotoluene is a raw material of organic synthesis, which can be used as the manufacture of p-bromobenzyl, p-bromodibromobenzyl and p-bromobenzaldehyde, etc.

Uses

4-Bromotoluene was used in the synthesis of ketones by Cu/Pd-catalyzed decarboxylative cross-coupling reaction. 4-Bromotoluene undergoes Heck reaction with styrene in the presence of in situ generated palladium complexes of phosphine-functionalized N-heterocyclic carbene ligands.

Preparation

4-Bromotoluene is prepared by diazotization and replacement of p-toluidine. First, add aqueous sulfuric acid solution to crushed p-toluidine while hot, cool to 5°C, and slowly add aqueous sodium nitrite solution until the starch potassium iodide test paper turns blue. Then add a small amount of urea to destroy the excess of sodium nitrite. Then add the synthesized cuprous bromide to hydrobromic acid, heat it to boiling, then slowly add the above diazo salt and distill it until no oil-like substance comes out. Wash, dry, filter, distill at atmospheric pressure and collect 183-185℃ fraction to obtain 4-Bromotoluene.

Synthesis Reference(s)

Organic Syntheses, Coll. Vol. 1, p. 136, 1941Tetrahedron, 64, p. 4999, 2008 DOI: 10.1016/j.tet.2008.03.085

General Description

Crystals, clear pale yellow liquid.

Air & Water Reactions

Insoluble in water.

Reactivity Profile

4-Bromotoluene is incompatible with strong oxidizing agents.

Fire Hazard

4-Bromotoluene is combustible.

Safety Profile

Moderately toxic by inhalation and intraperitoneal routes. When heated to decomposition it emits toxic vapors of Br-.

Purification Methods

Crystallise it from EtOH [Taylor & Stewart J Am Chem Soc 108 6977 1986]. [Beilstein 5 IV 827.]

InChI:InChI:1S/C7H7Br/c1-6-2-4-7(8)5-3-6/h2-5H,1H3

Upstream product

• 108-32-7 1,2-propylene cyclic carbonate 
• 128-08-5 N-Bromosuccinimide 
• 118-75-2 chloranil 
• 108-88-3 toluene 
• 94-36-0 dibenzoyl peroxide 
• 31543-75-6 2,4-dibromotoluene 
• 106-49-0 p-toluidine 
• 104-15-4 toluene-4-sulfonic acid 
• 537-64-4 bis(p-tolyl)mercury 
• 685-87-0 Diethyl 2-bromomalonate 
• 36719-51-4 3,3-diethyl-1-(4-methylphenyl)-1-triazene 
• 874-60-2 4-methyl-benzoyl chloride 
• 99-94-5 p-Toluic acid 
• 76-05-1 trifluoroacetic acid 

Downstream Products

• 5440-76-6 (4-methylphenyl)diphenylmethanol 
• 70401-28-4 2,9-dimethylacridine 
• 132594-51-5 2,2-bis-(5-bromo-2-methyl-phenyl)-1,1,1-trichloro-ethane 
• 19934-95-3 (phenyl)di(4-methylphenyl)phosphine 
• 1031-93-2 diphenyl(p-tolyl)phosphine 
• 106-42-3 para-xylene 
• 76978-38-6 (E)-5-(4-methylphenyl)-4-penten-1-ol 
• 97015-88-8 3-phenyl-4-phenylazo-5-p-tolyl-isoxazole 
• 3363-80-2 4-cyclohexyl-1-p-tolyl-cyclohexene 
• 93570-26-4 4-Methyl-1-p-tolyl-cyclohexanol 
• 1016-80-4 chloro-phenyl-p-tolyl-phosphine 
• 22975-58-2 1-methyl-4-(1'-ethyl)propylbenzene 
• 58824-48-9 1-(4-methylphenyl)-2-propen-1-ol 
• 14161-67-2 1-methyl-4-(2-methyl-1-phenylprop-1-en-1-yl)benzene 

Relevant articles and documents

Novel site-specific one-step bromination of substituted benzenes

Regiospecific bromination of benzene derivatives has been carried out with Me2SO-HBr; this method gives excellent yields of 2-bromobenzaldehyde and 2-bromonitrobenzene; strong ortho- and para-directing monosubstituted benzenes give para-bromo derivatives; a general discussion of the mechanism of these reactions is given.

Selective Halogenation of Aromatic Hydrocarbons with Alumina-Supported Copper(II) Halides

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Deoxygenation of carbonyl compounds using an alcohol as an efficient reducing agent catalyzed by oxo-rhenium complexes

This work describes the first methodology for the deoxygenation of carbonyl compounds using an alcohol as a green solvent/reducing agent catalyzed by oxo-rhenium complexes. The system 3-pentanol/ReOCl3(SMe2)(OPPh3) was successfully employed in the deoxygenation of several aryl ketones to the corresponding alkenes and also in the deoxygenation of aryl aldehydes to alkanes with moderate to excellent yields. The catalyst ReOCl3(SMe2)(OPPh3) can also be used in several catalytic cycles with good activity.

A new method of bromination of aromatic rings by an iso-amyl nitrite/HBr system

A mixture of iso-amyl nitrite/HBr is shown to be a mild and efficient reagent for electrophilic aromatic bromination. The reaction succeeds with slightly activated arenes and heterocyclic compounds. By using HCl instead of HBr, chlorination can also be performed in few cases. The i-amONO2/HBr mixture can also be utilized for bromination in the α-position of electron withdrawing groups. A possible mechanism is briefly discussed.

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Bipyridinium and Phenanthrolinium Dications for Metal-Free Hydrodefluorination: Distinctive Carbon-Based Reactivity

The development of novel Lewis acids derived from bipyridinium and phenanthrolinium dications is reported. Calculations of Hydride Ion Affinity (HIA) values indicate high carbon-based Lewis acidity at the ortho and para positions. This arises in part from extensive LUMO delocalization across the aromatic backbones. Species [C10H6R2N2CH2CH2]2+ (R=H [1 a]2+, Me [1 f]2+, tBu [1 g]2+), and [C12H4R4N2CH2CH2]2+ (R=H [2 a]2+, Me [2 b]2+) were prepared and evaluated for use in the initiation of hydrodefluorination (HDF) catalysis. Compound [2 a]2+ proved highly effective towards generating catalytically active silylium cations via Lewis acid-mediated hydride abstraction from silane. This enabled the HDF of a range of aryl- and alkyl- substituted sp3(C?F) bonds under mild conditions. The protocol was also adapted to effect the deuterodefluorination of cis-2,4,6-(CF3)3C6H9. The dications are shown to act as hydride acceptors with the isolation of neutral species C16H14N2 (3 a) and C16H10Me4N2 (3 b) and monocationic species [C14H13N2]+ ([4 a]+) and [C18H21N2]+ ([4 b]+). Experimental and computational data provide further support that the dications are initiators in the generation of silylium cations.

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Halogenation Using N-Halogenocompounds. II. Acid Catalyzed Bromination of Aromatic Compounds with 1,3-Dibromo-5,5-dimethylhydantoin

Ring bromination of aromatic compounds using 1,3-dibromo-5,5-dimethylhydantoin in dichloromethane is promoted by the addition of strong acids.Both organic and inorganic acids whose pKa values are lower than -2 showed the promoting effect.This acid-catalyzed bromination is both practical and effective, even for aromatics having electron-withdrawing substituents.

Convenient Synthesis of Aryl Halides from Arylamines via Treatment of 1-Aryl-3,3-dialkyltriazenes with Trimethylsilyl Halides

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Room-temperature catalytic hydrodefluorination of C(sp3)-F bonds

Room-temperature catalytic hydrodefluorination of the strong C(sp3)-F bonds in benzotrifluorides and fluoropentane is catalyzed by Et3Si[B(C6F5)4] and uses Et3SiH as the source of H. Ar-CF

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OOxidative bromination of activated aromatic compounds using aqueous nitric acid as an oxidant

Oxidative bromination of activated aromatic compounds using alkali metal bromide salts and aqueous nitric acid to the corresponding bromo-derivatives is achieved in a liquid-liquid, two-phase system under ambient conditions. Nitric acid offers a dual function of an oxidant as well as a proton donor, which is essential for oxidative bromination using metal bromide salts. Bromination as well as chlorination could be accomplished with this simple system.

Reactions of benzyltriphenylphosphonium salts under photoredox catalysis

The development of benzyltriphenylphosphonium salts as alkyl radical precursors using photoredox catalysis is described. Depending on substituents, the benzylic radicals may couple to form C-C bonds or abstract a hydrogen atom to form C-H bonds. A natural product, brittonin A, was also synthesized using this method.

Mixed Micelles of Surface Active Ionic Liquid (SAIL)–Octylphenol Ethoxylate: A Novel Reaction Medium for Selective Oxidation of Toluene to Benzaldehyde

Ionic liquids have been found to be suitable alternatives to volatile organic solvents in chemical transformation. Through a proper choice of cations and anions, the properties of an ionic liquid can be tuned so that it resembles an amphiphile. Such specially designed molecules are known as surface-active ionic liquids (SAIL). Like conventional surfactants, SAIL also form aggregates in an aqueous medium. Studies show that the mixing of SAIL with conventional surfactants leads to synergistic micellization. However, very few reports are available on the application of such systems as reaction media. Present study focuses on the application of mixed micelles of 1-tetradecyl-3-methylimidazol-1-ium bromide, ([C14mim]Br) with nonionic surfactant, Octylphenol ethoxylate with 10 moles of ethylene oxide (OPE-10). Enhanced solubilization and selective catalytic oxidation of toluene using hydrogen peroxide as an oxidant and tungstic acid as a catalyst have been studied in detail using this system.

Hydrogen-Bond-Donor Solvents Enable Catalyst-Free (Radio)-Halogenation and Deuteration of Organoborons

A hydrogen bond donor solvent assisted (radio)halogenation and deuteration of organoborons has been developed. The reactions exhibited high functional group tolerance and needed only an ambient atmosphere. Most importantly, compared to literature methods, our conditions are more consistent with the principals of green chemistry (e.g., metal-free, strong oxidant-free, more straightforward conditions).