Safer way to make diazomethane developed

Mar 23, 2012 by Lin Edwards report
diazomethane

(PhysOrg.com) -- Diazomethane is a toxic, explosive reagent prepared as needed in laboratories, where it is commonly used in cyclopropanation, but its explosive nature prevents it being used widely on an industrial scale. Now, scientists in Switzerland have developed a new method of synthesising diazomethane that is much safer and therefore could lead to much wider use.

Diazomethane (CH2N2) is a toxic yellow gas at 25 degrees Celsius, and is usually used in solution in ether. It is a useful reagent for many reasons, such as its ability to be converted to , which is used in the synthesis of cyclopropanes. It is usually prepared as needed in the lab by hydrolysis of a precursor such as diazald (N-methyl-N-nitroso-p-toluenesufonamide), but becomes explosive during the processes of purifying and isolating it. Safety precautions such as preparing the chemical in a fume hood or behind a blast shield, avoiding ground glass joints, wearing thick , avoiding any sharp edges or scratches on the glassware, and so on, are employed during the synthesis to protect the scientists from potential explosions.

Researchers Erick Carreira and Bill Morandi of the Laboratory of at ETH in Zurich have developed a new method for generating diazomethane in situ that uses a catalyst and avoids the need for the dangerous isolation process and generation of large volumes of the explosive chemical. The catalyst is an iron porphyrin complex and is used to catalyze the cyclopropanation of olefins such as styrenes, dienes, and enynes in an of (6M, KOH). Since are immiscible with water, they create a safe biphasic environment for the formation of the intermediate, diazomethane, which is constantly generated and immediately consumed in the reaction. The catalyst remains within the olefin phase.

The new method is safer for the chemists because there is a much lower risk of explosion since the diazomethane is consumed as soon as it is created, and large volumes do not accumulate. There is also a much lower chance of exposure to the toxic gas.

In the paper, published in Science, Carreira and Morandi suggest the method could also be used in the synthesis of other toxic or explosive reagents, provided they can be prepared in aqueous solutions.

Explore further: Recycling industrial waste water: Scientists discover a new method of producing hydrogen

More information: Iron-Catalyzed Cyclopropanation in 6 M KOH with in Situ Generation of Diazomethane, Science 23 March 2012: Vol. 335 no. 6075 pp. 1471-1474, DOI: 10.1126/science.1218781

ABSTRACT
Diazomethane is a common and versatile reagent in organic synthesis whose broader use is generally impeded by its explosiveness and toxicity. Here we report that a simple iron porphyrin complex catalyzes the cyclopropanation of styrenes, enynes, and dienes under the demanding conditions [aqueous 6 molar potassium hydroxide (KOH) solution, open to air] necessary for the in situ generation of diazomethane from a water-soluble diazald derivative. A biphasic reaction medium arising from the immiscibility of the olefin substrates with water appears essential to the overall efficiency of the process. The work we describe highlights an approach to catalysis with untoward reactive intermediates, in which the conditions for their generation under operationally safe regimes dictate catalyst selection.

Related Stories

Microscale Chemical Factory

Jul 04, 2007

Miniaturization is invading the world of chemical syntheses. Since typical chemical syntheses take place in several reaction steps with various separation or purification steps in between, microchemistry has almost always ...

Metal-free catalyst shielding studied

Sep 06, 2006

U.S. scientists say they've found a simple metal free catalyst that can shield a specific alcohol without modifying another nearby alcohol.

Recommended for you

A greener source of polyester—cork trees

Apr 16, 2014

On the scale of earth-friendly materials, you'd be hard pressed to find two that are farther apart than polyester (not at all) and cork (very). In an unexpected twist, however, scientists are figuring out ...

A beautiful, peculiar molecule

Apr 16, 2014

"Carbon is peculiar," said Nobel laureate Sir Harold Kroto. "More peculiar than you think." He was speaking to a standing-room-only audience that filled the Raytheon Amphitheater on Monday afternoon for the ...

Metals go from strength to strength

Apr 15, 2014

To the human hand, metal feels hard, but at the nanoscale it is surprisingly malleable. Push a lump of metal with brute force through a right-angle mould or die, and while it might look much the same to the ...

User comments : 0

More news stories

Hackathon team's GoogolPlex gives Siri extra powers

(Phys.org) —Four freshmen at the University of Pennsylvania have taken Apple's personal assistant Siri to behave as a graduate-level executive assistant which, when asked, is capable of adjusting the temperature ...

Better thermal-imaging lens from waste sulfur

Sulfur left over from refining fossil fuels can be transformed into cheap, lightweight, plastic lenses for infrared devices, including night-vision goggles, a University of Arizona-led international team ...

Researchers discover target for treating dengue fever

Two recent papers by a University of Colorado School of Medicine researcher and colleagues may help scientists develop treatments or vaccines for Dengue fever, West Nile virus, Yellow fever, Japanese encephalitis and other ...