Telomerization (dimerization)
Encyclopedia
The telomerization is the linear dimerization of 1,3-dienes with simultaneous addition of a nucleophile
in a catalytic reaction.
and Takahashi at the Osaka University
in the late sixties. The general reaction equation is as follows:
The formation of several isomers are possible. In addition to 1,3-butadiene
also substituted dienes such as isoprene
or cyclic dienes such as cyclopentadiene
can be used. A variety of substances such as water
, ammonia
, alcohol
s, or C-H-acidic compounds can be used as nucleophile
s. When water is used, for example di-unsaturated alcohols are obtained.
The catalysts used are mainly metal-organic palladium
and nickel
compounds. In 1991, Kuraray implemented the
production of 1-octanol on an industrial scale (5000 t a(-1)).
The commercial route to produce 1-octene
based on butadiene as developed by Dow Chemical came on stream in Tarragona in 2008. The telomerization of butadiene with methanol
in the presence of a palladium catalyst yields 1-methoxy-2,7-octadiene, which is fully hydrogenated to 1-methoxyoctane in the next step. Subsequent cracking of 1-methoxyoctane gives 1-octene and methanol for recycle.
Nucleophile
A nucleophile is a species that donates an electron-pair to an electrophile to form a chemical bond in a reaction. All molecules or ions with a free pair of electrons can act as nucleophiles. Because nucleophiles donate electrons, they are by definition Lewis bases.Nucleophilic describes the...
in a catalytic reaction.
Reaction
The reaction was independently discovered by E. J. Smutny at ShellShell Oil Company
Shell Oil Company is the United States-based subsidiary of Royal Dutch Shell, a multinational oil company of Anglo Dutch origins, which is amongst the largest oil companies in the world. Approximately 22,000 Shell employees are based in the U.S. The head office in the U.S. is in Houston, Texas...
and Takahashi at the Osaka University
Osaka University
, or , is a major national university located in Osaka, Japan. It is the sixth oldest university in Japan as the Osaka Prefectural Medical College, and formerly one of the Imperial Universities of Japan...
in the late sixties. The general reaction equation is as follows:
The formation of several isomers are possible. In addition to 1,3-butadiene
1,3-Butadiene
1,3-Butadiene is a simple conjugated diene with the formula C4H6. It is an important industrial chemical used as a monomer in the production of synthetic rubber. When the word butadiene is used, most of the time it refers to 1,3-butadiene....
also substituted dienes such as isoprene
Isoprene
Isoprene , or 2-methyl-1,3-butadiene, is a common organic compound with the formula CH2=CCH=CH2. Under standard conditions it is a colorless liquid...
or cyclic dienes such as cyclopentadiene
Cyclopentadiene
Cyclopentadiene is an organic compound with the formula C5H6. This colorless liquid has a strong and unpleasant odor. At room temperature, this cyclic diene dimerizes over the course of hours to give dicyclopentadiene via a Diels–Alder reaction...
can be used. A variety of substances such as water
Water
Water is a chemical substance with the chemical formula H2O. A water molecule contains one oxygen and two hydrogen atoms connected by covalent bonds. Water is a liquid at ambient conditions, but it often co-exists on Earth with its solid state, ice, and gaseous state . Water also exists in a...
, ammonia
Ammonia
Ammonia is a compound of nitrogen and hydrogen with the formula . It is a colourless gas with a characteristic pungent odour. Ammonia contributes significantly to the nutritional needs of terrestrial organisms by serving as a precursor to food and fertilizers. Ammonia, either directly or...
, alcohol
Alcohol
In chemistry, an alcohol is an organic compound in which the hydroxy functional group is bound to a carbon atom. In particular, this carbon center should be saturated, having single bonds to three other atoms....
s, or C-H-acidic compounds can be used as nucleophile
Nucleophile
A nucleophile is a species that donates an electron-pair to an electrophile to form a chemical bond in a reaction. All molecules or ions with a free pair of electrons can act as nucleophiles. Because nucleophiles donate electrons, they are by definition Lewis bases.Nucleophilic describes the...
s. When water is used, for example di-unsaturated alcohols are obtained.
The catalysts used are mainly metal-organic palladium
Palladium
Palladium is a chemical element with the chemical symbol Pd and an atomic number of 46. It is a rare and lustrous silvery-white metal discovered in 1803 by William Hyde Wollaston. He named it after the asteroid Pallas, which was itself named after the epithet of the Greek goddess Athena, acquired...
and nickel
Nickel
Nickel is a chemical element with the chemical symbol Ni and atomic number 28. It is a silvery-white lustrous metal with a slight golden tinge. Nickel belongs to the transition metals and is hard and ductile...
compounds. In 1991, Kuraray implemented the
production of 1-octanol on an industrial scale (5000 t a(-1)).
The commercial route to produce 1-octene
1-Octene
1-Octene is an organic compound with a formula CH2CHC6H13. The alkene is classified as a higher olefin and alpha-olefin, meaning that the double bond is located at the alpha position, endowing this compound with higher reactivity and thus useful chemical properties. 1-Octene is one of the...
based on butadiene as developed by Dow Chemical came on stream in Tarragona in 2008. The telomerization of butadiene with methanol
Methanol
Methanol, also known as methyl alcohol, wood alcohol, wood naphtha or wood spirits, is a chemical with the formula CH3OH . It is the simplest alcohol, and is a light, volatile, colorless, flammable liquid with a distinctive odor very similar to, but slightly sweeter than, ethanol...
in the presence of a palladium catalyst yields 1-methoxy-2,7-octadiene, which is fully hydrogenated to 1-methoxyoctane in the next step. Subsequent cracking of 1-methoxyoctane gives 1-octene and methanol for recycle.
External links
Literature
- P. Fischer: process concepts for the transition-telomerization of isoprene with water or methanol. Shaker Verlag, 2002, 176 pages, ISBN 3832204148, ISBN 978-3832204143
- EJ Smutny, J. Amer. Chem. 89 (1967) 6793
- S. Takahashi, Tetrahedron Lett. 1967, 2451
- A. Behr, M. Becker, T. Beckmann, L. Johnen, J. Leschinski, S. Reyer, Angew. Chem. Int. Ed. 2009, 48, 3598-3614
- M.J.-L. Tschan, E.J. Garcıa-Suarez, Z. Freixa, H. Launay, H. Hagen, J. Benet-Buchholz, P.W.N.M. van Leeuwen, J. Am. Chem. Soc. 2010, 132, 6463-6473.