1,2-diaminocyclohexane

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Structural formula
Structural formulas of (R, R) -1,2-diaminocyclohexane (top left), (S, S) -1,2-diaminocyclohexane (top right) and meso-1,2-diaminocyclohexane (bottom)
Structural formulas of ( R , R ) -1,2-diaminocyclohexane (top left), ( S , S ) -1,2-diaminocyclohexane (top right) and meso -1,2-diaminocyclohexane
General
Surname 1,2-diaminocyclohexane
other names
  • 1,2-cyclohexanediamine ( IUPAC )
  • TOP, ROOF
Molecular formula C 6 H 14 N 2
Brief description

colorless liquid with an amine-like odor

External identifiers / databases
CAS number
  • 694-83-7 (mixture of isomers)
  • 1121-22-8 ( mixture of trans isomers)
  • 1436-59-5 ( cis isomer = meso form)
  • 20439-47-8 [(1 R , 2 R ) - (-) - enantiomer]
  • 21436-03-3 [(1 S , 2 S ) - (+) - enantiomer]
EC number 606-765-2
ECHA InfoCard 100.127.756
PubChem 479307
ChemSpider 420572
Wikidata Q161459
properties
Molar mass 114.19 g mol −1
Physical state

liquid

density

0.95 g cm −3

boiling point

183 ° C

Vapor pressure

11.5 h Pa (70 ° C)

solubility

soluble in water

safety instructions
GHS labeling of hazardous substances
05 - Corrosive 07 - Warning

danger

H and P phrases H: 302-312-332-314-335
P: 301 + 330 + 331-280-305 + 351 + 338-310
As far as possible and customary, SI units are used. Unless otherwise noted, the data given apply to standard conditions .

1,2-Diaminocyclohexane is a chemical compound . It consists of a cyclohexane ring as the basic structure, to which two amino groups are bonded to adjacent carbon atoms and thus belongs to the group of diamines .

Isomerism

1,2-Diaminocyclohexane contains two stereogenic centers, consequently there are three stereoisomers: ( R , R ) -1,2-diaminocyclohexane and the mirror image of ( S , S ) -1,2-diaminocyclohexane and meso -1,2-diaminocyclohexane . The 1: 1 mixture of ( R , R ) - and the enantiomeric ( S , S ) form is the racemate trans -1,2-diaminocyclohexane. Meso -1,2-diaminocyclohexane is sometimes also called cis -1,2-diaminocyclohexane.

presentation

1,2-Diaminocyclohexane can be produced by Curtius degradation of 1,2-cyclohexanedicarboxylic acid. If the trans -1,2-cyclohexanedicarboxylic acid is used as the starting material, the amino groups in the product are also arranged in the trans position. Starting from cis- 1,2-cyclohexanedicarboxylic acid ( meso- 1,2-cyclohexanedicarboxylic acid), cis- 1,2-diaminocyclohexane ( meso- 1,2-diaminocyclohexane) is obtained analogously . The resolution of trans -1,2-diaminocyclohexane [1: 1 mixture of ( R , R ) -1,2-diaminocyclohexane and ( S , S ) -1,2-diaminocyclohexane] into its enantiomers can be carried out via diastereomeric salts manage the treatment with enantiomerically pure tartaric acid .

The cis -1,2-diaminocyclohexane (in the form of its sulfate salt) can be obtained from the isomer mixture by reaction with nickel chloride and subsequent treatment with sulfuric acid and ethanol.

properties

It is a colorless compound that is liquid at room temperature and boils at 183 ° C. The rotation of the pure substance at 55 ° C and a wavelength of 589 nm is −36 ° [( R , R ) -enantiomer].

use

Through condensation reactions with α, β- diketones , 1,2-diaminocyclohexane can be used for the synthesis of pyrazines . With elimination of two water molecules are so initially diimine obtained, which then pyrazines oxidized can be.

By condensation with activated carboxylic acids ( Steglich esterification ) or carboxylic acid chlorides can amides are prepared. This reaction is used, for example, to synthesize the Trost ligand .

Synthesis of the Trost ligand from 2-diphenylphosphinocarboxylic acid, trans -1,2-diaminocyclohexane, dicyclohexylcarbodiimide and 4-dimethylaminopyridine in dichloromethane .

In complex chemistry , 1,2-diaminocyclohexane can be used as a bidentate chelating ligand . For example, oxaliplatinous compounds that are used as cytostatics are platinum complexes of 1,2-diaminocyclohexane.

Structure of an oxaliplatinum complex

In addition, 1,2-diaminocyclohexane condenses with two equivalents of a salicylaldehyde derivative to form a salen ligand . These tetradentate chelating ligands form with cobalt (II) complexes , as oxygen transporters , for example, in the Jacobsen epoxidation used.

Individual evidence

  1. ↑ a b c d e data sheet 1,2-diaminocyclohexane (PDF) from Merck , accessed on January 18, 2011.
  2. ↑ a b Entry on cyclohex-1,2-ylenediamine in the GESTIS substance database of the IFA , accessed on February 8, 2018(JavaScript required) .
  3. ^ Heinrich Otto Wieland , Otto Schlichting, Werner von Langsdorff: Hoppe-Seyler's Journal for Physiological Chemistry , Vol. 161 (1926), p. 76, ISSN  0018-4888 .
  4. ^ A b F. M. Jaeger, Lucas Bijkerk: About complex salts of trivalent cobalt, chromium and rhodium with racemic and optically active trans-cyclohexane-1,2-diamines . In: Journal for inorganic and general chemistry , Vol. 233 (1937), pp. 97-139. ISSN  0044-2313 , doi: 10.1002 / zaac.19372330202 .
  5. ↑ Prisca K. Eckert, Verena Schill, Carsten Strohmann: Synthesis of cis-TMCDA: Optimization and characterization of a key intermediate . In: Inorganica Chimica Acta . 2011, doi : 10.1016 / j.ica.2011.06.008 .
  6. ↑ Bernhard Johannes Lüssem: Palladium-catalyzed enantioselective synthesis of allylic thiocarboxylates and palladium-catalyzed deracemization of allylic carbonates (PDF; 7.8 MB) . Dissertation, RWTH Aachen 2004.
  7. ↑ Konstantin P. Bryliakov, Evgenij P. Talsi: European Journal of Organic Chemistry , Vol. 11 (2008), pp. 3369-3376, ISSN  1099-0690 .