1,5,9-cyclododecatriene

Structural formula
	1,5,9-cyclododecatriene; a) trans , trans , trans -isomer ( E , E , E -isomer) ; b) cis , trans , trans -isomer ( Z , E , E -isomer) ; c) cis , cis , trans -isomer ( Z , Z , E isomer) ; d) cis , cis , cis isomer ( Z , Z , Z isomer)
General
Surname	1,5,9-cyclododecatriene
other names	Cyclododeca-1,5,9-triene; Cyclododecatriene; CDT;
Molecular formula	C 12 H 18
Brief description	colorless to yellowish liquid with a pungent odor
External identifiers / databases
EC number	225-533-8
ECHA InfoCard	100.023.212
PubChem	12668
Wikidata	Q61739965
properties
Molar mass	162.27 g mol −1
Physical state	liquid
density	0.8925 g cm −3 ( E , Z , Z ) ; 0.8895 g cm −3 ( E , E , Z )
Melting point	−1.5 ° C ( Z , Z , Z ) ; 31–32 ° C ( E , E , E ) ; −9 - −8 ( E , Z , Z ) ; −18 ° C ( E , E , Z )
boiling point	108 ° C (2266 Pa) ( Z , Z , Z ) ; 237.5 ° C ( E , E , E ) ; 224 ° C ( E , Z , Z ) ; 241.5 ° C ( E , E , Z )
Vapor pressure	0.1 mbar (20 ° C)
solubility	practically insoluble in water (5 mg l −1 at 20 ° C)
Refractive index	1.5005 ( E , E , E ) ; 1.5129 ( E , Z , Z ) ; 1.5061 ( E , E , Z )
safety instructions
H and P phrases	H: 304-410
	P: 273-301 + 310-331-391-405-501
Toxicological data	1780 mg kg −1 ( LD 50 , rat , oral )
	As far as possible and customary, SI units are used. Unless otherwise noted, the data given apply to standard conditions . Refractive index: Na-D line , 20 ° C

1,5,9-Cyclododecatriene (CDT) is a chemical compound from the group of unsaturated cyclic hydrocarbons , more precisely the cycloalkenes , with three double bonds , which occurs in four isomeric forms.

Occurrence

Cyclododecatriene is a starting material and the main breakdown product of hexabromocyclododecane (HBCDD).

Extraction and presentation

The industrially important 1,5,9 trans - trans - cis - isomer [( E , E , Z ) isomer] can be obtained by cyclotrimerization of 1,3-butadiene with titanium tetrachloride and the organoaluminum - Co-catalyst Al (C ₂ H ₅ ) Cl ₂ -Al (C ₂ H ₅ ) Cl _{2 can be obtained} with an overall selectivity of over 90%.

In the presence of nickel or chromium catalysts, the cyclotrimerization leads preferentially to the 1,5,9- trans - trans - trans - isomer [( E , E , E ) -isomer].

use

Cyclododecatriene is used as an intermediate in the production of chemical compounds such as additives in building materials, fillers and insulation materials, resin for styrene-butadiene rubber , lubricants, fragrances, adhesives and as stabilizers and plasticizers for thermoplastic polymers.

It is used as the starting material for the production of 1,12-dodecanedioic acid (which is used in the production of polyamides ) by hydrogenation to cyclododecane (2) followed by oxidation in the presence of boric acid . This creates an alcohol (3a) and a ketone (3b), which are further reacted with nitric acid to form 1,12-dodecanedioic acid (4):

The complete bromination produces the hexabromocyclododecane used as a flame retardant .

safety instructions

1,5,9-Cyclododecatriene forms flammable vapor-air mixtures at elevated temperatures. With flash points of 88 ° C for a mixture of isomers, 81 ° C for the ( E , E , E ) -isomer and 93 ° C for the ( E , E , Z ) -isomer, the substance is considered to be flame-retardant. The explosion range is between 1 vol.% As the lower explosion limit (LEL) and 4 vol.% As the upper explosion limit (UEL). The ignition temperature is 244 ° C. The substance therefore falls into temperature class T3.

Accident in CDT production in Marl

In Germany, CDT is produced by Evonik Industries in the Marl Chemical Park . On March 31, 2012, a serious fire broke out in the facility, as a result of which two workers died. According to investigations, the cause of the fire is assumed to be an overdose of a catalyst. The failure of the plant temporarily led to delivery bottlenecks for CDT-based products, which mainly affected the automotive and photovoltaic industries.

Web links

GPS Safety Summary Cyclododeca-1,5,9-triene. (PDF; 118 kB) Retrieved May 23, 2012

Individual evidence

↑ ^a ^b ^c ^d ^e ^f ^g ^h ⁱ Entry on Cyclododeca-1,5,9-triene in the GESTIS substance database of the IFA , accessed on February 1, 2016(JavaScript required) .
^ NN Greenwood, JH Morris: 589. Boron-carbon heterocyclic compounds. Part I. Synthesis and reactions of perhydro-9b-boraphenalene . In: Journal of the Chemical Society (Resumed) . 1960, p. 2922 , doi : 10.1039 / JR9600002922 .
↑ ^a ^b ^c Hirosi Takahasi, Muneaki Yamaguchi: Synthesis of 1,5,9-Cyclododecatriene . In: The Journal of Organic Chemistry . tape 28 , no. 5 , 1963, pp. 1409-1411 , doi : 10.1021 / jo01040a519 .
↑ ^a ^b ^c ^d ^e Longiave et al .: Trimerizzarione ciclica del butadiene con catalizzatori solubili a base di titanio . In: Chimica e l'Industria . No. 49 , 1967, p. 497-498 .
↑ ^a ^b ^c ^d ^e By H. Breil, P. Heimbach, M. Kroener, H. Mueller, G. Wilke: Synthesis of cyclododecatrienes— (1,5,9). I. Mitt. On the catalytic conversion of olefins . In: The Macromolecular Chemistry . tape 69 , no. 1 , 1963, p. 18-40 , doi : 10.1002 / macp.1963.020690102 .
↑ Patent US3354229 : Oxonation of cyclododecatriene to C13 alcohol. Published November 21, 1967 , Applicant: Esso Research & Engineering, Inventor: Neville L. Cull, Lloyd A. Pine. ‌
↑ Hexabromocyclododecane as a possible global POP. (PDF; 802 kB) Nordic Council of Ministers, 2008, p. 28 , accessed on May 23, 2012 (English).
↑ Entry on 1,5,9-cyclododecatriene. In: Römpp Online . Georg Thieme Verlag, accessed on October 22, 2015.
^ Klaus Weissermel , Hans-Jürgen Arpe : Industrial Organic Chemistry . 3rd ed., John Wiley & Sons, 1997, ISBN 3-527-28838-4 .
↑ ^a ^b G. Oenbrink, T. Schiffer: cyclododecatrienes, cyclooctadiene, and 4-vinylcyclohexenes in: Ullmann's Encyclopedia of Industrial Chemistry . Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim 2012, doi : 10.1002 / 14356007.a08_205.pub2 .
↑ Roland Streck, Herbert Hartig: Production and possible uses of cyclododecatriene and cyclooctadiene . In: Chemical Engineer Technology . tape 62 , no. 11 , 1990, pp. 888-891 , doi : 10.1002 / cite.330621105 .
^ ^A ^b ^c E. Brandes, W. Möller: Safety-related parameters - Volume 1: Flammable liquids and gases , Wirtschaftsverlag NW - Verlag für neue Wissenschaft GmbH, Bremerhaven 2003.
↑ Fire at the CDT plant on the grounds of the Marl Chemicals Park. Evonik Industries, April 4, 2012, accessed May 23, 2012 .
↑ Operating license for CDT plant in Marl issued by the Münster district government. Evonik Industries, December 4, 2012, accessed May 26, 2013 .
↑ Evonik incident makes car managers restless. (No longer available online.) In: automobil-produktion.de. April 18, 2012, archived from the original on April 29, 2012 ; Retrieved May 23, 2012 .

[GESTIS-1] ↑ ^a ^b ^c ^d ^e ^f ^g ^h ⁱ Entry on Cyclododeca-1,5,9-triene in the GESTIS substance database of the IFA , accessed on February 1, 2016(JavaScript required) .

[DOI10.1039/JR9600002922-2] NN Greenwood, JH Morris: 589. Boron-carbon heterocyclic compounds. Part I. Synthesis and reactions of perhydro-9b-boraphenalene . In: Journal of the Chemical Society (Resumed) . 1960, p. 2922 , doi : 10.1039 / JR9600002922 .

[DOI10.1021/jo01040a519-3] Hirosi Takahasi, Muneaki Yamaguchi: Synthesis of 1,5,9-Cyclododecatriene . In: The Journal of Organic Chemistry . tape 28 , no. 5 , 1963, pp. 1409-1411 , doi : 10.1021 / jo01040a519 .

[Longiave-4] Longiave et al .: Trimerizzarione ciclica del butadiene con catalizzatori solubili a base di titanio . In: Chimica e l'Industria . No. 49 , 1967, p. 497-498 .

[DOI10.1002/macp.1963.020690102-5] By H. Breil, P. Heimbach, M. Kroener, H. Mueller, G. Wilke: Synthesis of cyclododecatrienes— (1,5,9). I. Mitt. On the catalytic conversion of olefins . In: The Macromolecular Chemistry . tape 69 , no. 1 , 1963, p. 18-40 , doi : 10.1002 / macp.1963.020690102 .

[6] Patent US3354229 : Oxonation of cyclododecatriene to C13 alcohol. Published November 21, 1967 , Applicant: Esso Research & Engineering, Inventor: Neville L. Cull, Lloyd A. Pine. ‌

[norway_HBCDD-7] Hexabromocyclododecane as a possible global POP. (PDF; 802 kB) Nordic Council of Ministers, 2008, p. 28 , accessed on May 23, 2012 (English).

[Roempp-8] Entry on 1,5,9-cyclododecatriene. In: Römpp Online . Georg Thieme Verlag, accessed on October 22, 2015.

[Weissermel-9] Klaus Weissermel , Hans-Jürgen Arpe : Industrial Organic Chemistry . 3rd ed., John Wiley & Sons, 1997, ISBN 3-527-28838-4 .

[Ullmann-10] G. Oenbrink, T. Schiffer: cyclododecatrienes, cyclooctadiene, and 4-vinylcyclohexenes in: Ullmann's Encyclopedia of Industrial Chemistry . Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim 2012, doi : 10.1002 / 14356007.a08_205.pub2 .

[Streck_1990-11] Roland Streck, Herbert Hartig: Production and possible uses of cyclododecatriene and cyclooctadiene . In: Chemical Engineer Technology . tape 62 , no. 11 , 1990, pp. 888-891 , doi : 10.1002 / cite.330621105 .

[Brandes-12] A ^b ^c E. Brandes, W. Möller: Safety-related parameters - Volume 1: Flammable liquids and gases , Wirtschaftsverlag NW - Verlag für neue Wissenschaft GmbH, Bremerhaven 2003.

[evonik_press_release-13] Fire at the CDT plant on the grounds of the Marl Chemicals Park. Evonik Industries, April 4, 2012, accessed May 23, 2012 .

[Der_westen-14] Operating license for CDT plant in Marl issued by the Münster district government. Evonik Industries, December 4, 2012, accessed May 26, 2013 .

[Automobil-15] Evonik incident makes car managers restless. (No longer available online.) In: automobil-produktion.de. April 18, 2012, archived from the original on April 29, 2012 ; Retrieved May 23, 2012 .