115665-69-5

Usage

Physical state

Colorless liquid

Odor

Slightly sweet

Uses

a. Intermediate in the synthesis of pharmaceuticals
b. Intermediate in the synthesis of agrochemicals
c. Intermediate in the synthesis of other organic compounds
d. Solvent in organic synthesis
e. Reagent in organic synthesis
f. Production of polymers
g. Manufacturing of dyes and perfumes

Safety precautions

Toxic and may cause irritation to skin, eyes, and respiratory system

Upstream product

• 97065-56-0 1-(2,2-dibromovinyl)-3-methylbenzene 
• 3029-79-6 (E)-3-methylcinnamic acid 
• 620-23-5 m-tolyl aldehyde 
• 3029-79-6 3-methylcinnamic acid 
• 121139-31-9 2,3-dibromo-3-m-tolyl-propionic acid 
• 766-82-5 1-ethynyl-3-methyl-benzene 

Downstream Products

• 1370426-37-1 (Z)-1-(3-methylstyryl)-1H-imidazole 
• 1370426-38-2 (Z)-1-(3-methylstyryl)-1H-benzo[d]imidazole 
• 1607020-75-6 N-(4-methylphenyl)-3-exo-(3-methylbenzylidene)tricyclo[3.2.1.02,4]octane-6,7-endo-dicarboximide 
• 1607021-04-4 N-isobutyl-3-exo-(3-methylbenzylidene)tricyclo[3.2.1.02,4]octane-6,7-endo-dicarboximide 
• 1018680-78-8 methyl 5-(m-tolyl)isoxazole-3-carboxylate 
• 893638-47-6 ethyl 5-(3-methylphenyl)isoxazole-3-carboxylate 
• 1372768-19-8 (E)-(5-chloro-2-(4-m-tolylbut-3-en-1-ynyl)phenyl)diphenylsilanol 
• 1344730-55-7 (E)-1-(3-methylphenyl)-4-phenylbut-1-en-3-yne 
• 1133321-55-7 (E)-3,3'-(but-1-en-3-yne-1,4-diyl)bis(methylbenzene) 

Relevant academic research and scientific papers

Palladium(0)-Catalyzed Methylcyclopropanation of Norbornenes with Vinyl Bromides and Mechanism Study

An unusual methylcyclopropanation from [2 + 1] cycloadditions of vinyl bromides to norbornenes catalyzed by Pd(OAc)2/PPh3 in the presence of CH3ONa and CH3OH has been established. A methylcyclopropane subunit was installed by a 3-fold domino procedure involving a key protonation course. Preliminary deuterium-labeling studies revealed that the proton came from methyl of CH3OH and also exposed an additional hydrogen/deuterium exchange process. These two proton-concerned reactions were fully chemoselective.

Illuminatinganti-hydrozirconation: controlled geometric isomerization of an organometallic species

A general strategy to enable the formalanti-hydrozirconation of arylacetylenes is reported that mergescis-hydrometallation using the Schwartz Reagent (Cp2ZrHCl) with a subsequent light-mediated geometric isomerization atλ= 400 nm. Mechanistic delineation of thecontra-thermodynamic isomerization step indicates that a minor reaction product functions as an efficientin situgenerated photocatalyst. Coupling of theE-vinyl zirconium species with an alkyne unit generates a conjugated diene: this has been leveraged as a selective energy transfer catalyst to enableE→Zisomerization of an organometallic species. Through anUmpolungmetal-halogen exchange process (Cl, Br, I), synthetically useful vinyl halides can be generated (up toZ?:?E= 90?:?10). This enabling platform provides a strategy to access nucleophilic and electrophilic alkene fragments in both geometric forms from simple arylacetylenes.

Selective Rhodium-Catalyzed Hydroformylation of Terminal Arylalkynes and Conjugated Enynes to (Poly)enals Enabled by a π-Acceptor Biphosphoramidite Ligand

The hydroformylation of terminal arylalkynes and enynes offers a straightforward synthetic route to the valuable (poly)enals. However, the hydroformylation of terminal alkynes has remained a long-standing challenge. Herein, an efficient and selective Rh-catalyzed hydroformylation of terminal arylalkynes and conjugated enynes has been achieved by using a new stable biphosphoramidite ligand with strong π-acceptor capacity, which affords various important E-(poly)enals in good yields with excellent chemo- and regioselectivity at low temperatures and low syngas pressures.

Electrochemical intramolecular C-H/N-H functionalization for the synthesis of isoxazolidine-fused isoquinolin-1(2: H)-ones

A general and practical protocol for the construction of isoxazolidine-fused isoquinolin-1(2H)-ones has been described by electrochemical-oxidation-induced intramolecular annulation via amidyl radicals. In an undivided cell, isoquinolinones could be easily generated from various available amides bearing CONHOR groups under metal-free, additive-free and external oxidant-free conditions. Moreover, this transformation proceeded smoothly by using cheap 95% ethanol as the green solvent and could be extended to the gram scale.

Decarboxylative bromination of α,β-unsaturated carboxylic acids via an anodic oxidation

A novel bromination of α,β-unsaturated carboxylic acids was developed via a decarboxylation by virtue of a direct anodic electro-oxidation. In this method, ammonium bromide was employed as a bromine source and the reaction features transition-metal-free, short time, and no additional supporting electrolyte.

Palladium-Catalyzed Two-Component Domino Coupling Reaction of (Z)-β-Bromostyrenes with Norbornenes: Synthesis of 1,5-Enynes

Polyfunctional molecules, 1,5-enynes, have been achieved via a palladium(0)-catalyzed domino coupling reaction of (Z)-β-bromostyrenes with norbornenes in the presence of cesium carbonate and N,N-dimethylformamide. The process involves a double Heck-type procedure, two-fold C(sp2) H activation and formation of two carbon-carbon bonds. There are possibilities of diversified transformation for the domino coupling of (Z)-β-bromostyrenes with norbornenes, the procedure is successfully driven to 1,5-enynes via accurate adjustment of the reaction conditions. (Figure presented.) .

Catalytic anti-Markovnikov hydrobromination of alkynes

We have developed the first catalytic method for anti-Markovnikov hydrobromination of alkynes. The reaction affords terminal E-alkenyl bromides in high yield and with excellent regio- and diastereoselectivity. Both aryl- and alkyl-substituted terminal alkynes can be used as substrates. Furthermore, the reaction conditions are compatible with a wide range of functional groups, including esters, nitriles, epoxides, aryl boronic esters, terminal alkenes, silyl ethers, aryl halides, and alkyl halides. A preliminary study of the reaction mechanism suggests that the hydrobromination reaction involves hydrocupration of an alkyne, followed by the bromination of the alkenyl copper intermediate. This study also suggests that 2-tert-butyl potassium phenoxide functions as a mild catalyst turnover reagent and provides a better understanding of the unique effectiveness of (BrCl2C)2 among brominating reagents.

H-β-zeolite catalyzed synthesis of β-bromostyrenes from styrene bromohydrins

Synthesis of β-bromostyrenes from styrene bromohydrins using H-β-zeolite as catalyst under moderate conditions is reported. The catalyst could be regenerated and reused up to three consecutive cycles.

Palladium(0)-catalyzed methylenecyclopropanation of norbornenes with vinyl bromides

Highly strained methylenecyclopropane derivatives have been achieved via a novel and efficient Pd(0)-catalyzed domino reaction. The formal [2 + 1] cycloaddition reaction of vinyl bromides to norbornenes involves a Heck-type coupling and a C(sp2)-H bond activation.

Palladium-catalyzed [2+1+1] annulation of norbornenes with (z)-bromostyrenes: Synthesis of bismethylenecyclobutanes via twofold C(sp2)-H bond activation

The first Pd-catalyzed intermolecular [2+1+1] annulation reaction of (Z)-bromostyrene derivatives and norbornenes has been realized. Bismethylenecyclobutane derivatives were obtained with high yields. The domino coupling reaction involves a double Heck-type coupling process, twofold C(sp2)-H bond activation and formation of three carbon-carbon bonds.