Bromomethyl Substituted compounds

Halomethyl derivatives have been proved to be valuable intermediates for the preparation of catalysts and active substances, for example plant protection agents, dyes and polymers to pharmaceuticals. Among them, bromomethyl aromatics are a particular class, due to its higher reactivity than chloromethyl aromatics. Bromomethyl aromatics are not only more easily converted into alcohols, aldehydes, amine, carboxylic acids, esters, acrylic and metal organic compounds, but also very useful for some of difficult synthesis reactions with chloromethyl aromatics. Consequently, a sustained interest has been focused on the bromomethylated aromatics preparation. In general, bromomethyl compounds can be prepared either from a direct bromination of the corresponding aromatic methyl compounds, or from a deoxybromination of benzylic alcohol.

more...

  Synthesis of Bromomethyl Substituted compounds

1.

 

Methyl 3-methyl-benzoate (15.0 g, 0.1 mol) was dissolved in 150 mL carbon tetrachloride and N-bromosuccinimide (20.0 g, 0.11 mol) was added. The mixture was refluxed for 6 h accompanied with illumination and the white succinimide residue was filtered off. The solvent was evaporated under reduced pressure to give a yellow liquid, which was purified with ether at -78 deg C to get 4a as a yellow liquid at room temperature (21.6 g, 94.3% yield).

2

Phosphorous tribromide (2.04 g, 7.52 mmol) was added to a stirred solution of 2-methoxybenzyl alcohol (3.00 g, 21.5 mmol) and toluene (25 mL) at 40 deg C. The solution was heated to 100 deg C for 10 min, and the reaction was cooled to ambient temperature. The liquid was decanted and washed with water (2 X 50 mL) and brine (50 mL). The combined aqueous washes were extracted with ether (75 mL), and the combined organic fractions were spin evaporated to give 4.9 g of a semisolid residue. The residue was dissolved in ether (100 mL) and washed with water (2 X 50 mL) and brine (50 mL). The organic phase was spin evaporated to an oil, which was repeatedly coevaporated with toluene to give 4.04 g (94%) of 2-methoxybenzyl bromide as a golden oil.

3.

To a solution of I01-5816 (2.0 g, 9.3 mmol, 1.0 equiv) in CH2Cl2 (60 mL) at 0 °C was added PPh3 (3.67 g, 14.0 mmol, 1.5 equiv) and CBr4 (4.64 g, 14.0 mmol, 1.5 equiv). After 30 min the reaction was concentrated in-vacuo, then the residue was taken up in Et2O (50 mL) and placed at -20 °C for 30 min. The solution was filtered to remove solid Ph3PO and the filtrate was concentrated under reduced pressure. Purification by flash chromatography (hexanes/EtOAc) afforded the title compound (2.28 g, 88%).

 

The application of Bromomethyl Substituted compounds

1.


    Tetrahedron Lett.,2011, 1574 â€?1577

2.


    Eur. J. Med. Chem.,2011,1207 â€?1221

3.


    Bioorg. Med. Chem.,2009, 17,1307-1324

4.


    J. Chem. Soc. 1951, 2430-2440

 

 

 we deliver an innovative chemical database for your commercial sourcing

placing enquiry and order

over 25 kilo chemicals are available here for commercial sourcing.

enquiry can be placed on-line at http://www.ispharm.com/ or http://www.is-pharm.com/, by mailing to sales@ispharm.com or info@ispharm.com, and fax to +86 21 52685809.

we receive the order sent via the email and fax and the payment by paypal, credit card and t/t.

useful search functions online

search for the product by structure at http://www.ispharm.com/structure/search.html

search the cofa of the product online at homepage of http://www.ispharm.com/

search msds on the right side of the general information of every product

check the updated status of your order at http://www.ispharm.com/order/order_status.html

download our product list at http://www.ispharm.com/download/download.html

quality control

the standardization laboratory of is chemical technology in jinshan district, shanghai city, will provide the quality assurance for you. before delivery, all products pass through the structure identification and assay checking, and are attached with coa, nmr report and msds.

shipping and handling

is chemical technology commits to make every effort to ensure the delivery on schedule.

we use air express, such as fedex, dhl and ems, for most packages, and rate varies depend on location, package weight, and shipping type etc.

international shipping charge,

$45-55/per package (quantity: <0.5kg);

poa for quantities over 0.5 kg

credit

is chemical technology pays more attention to the business credit and has been devoting to establish sincere and faithful business relation with the partners. in 2009, is chemical technology took the lead in cooperating with dun & bradstreet, the world leading credit management and consulting agency, participating in the d&b d-u-n-s registered program of the company.