Triisopropylamine

Triisopropylamine is an organic chemical compound consisting of three isopropyl groups bound to a central nitrogen atom.[1][2] As a hindered tertiary amine, it can be used as a non-nucleophilic base and as a stabilizer for polymers; however, its applications are limited by its relatively high cost and difficult synthesis.

Triisopropylamine
Skeletal formula of triisopropylamine
Names
Preferred IUPAC name
N,N-Di(propan-2-yl)propan-2-amine
Other names
Tri(propan-2-yl)amine
(Triisopropyl)amine
Identifiers
3D model (JSmol)
ChemSpider
ECHA InfoCard 100.020.289 Edit this at Wikidata
EC Number
  • 222-317-5
UNII
  • InChI=1S/C9H21N/c1-7(2)10(8(3)4)9(5)6/h7-9H,1-6H3 ☒N
    Key: RKBCYCFRFCNLTO-UHFFFAOYSA-N ☒N
  • CC(C)N(C(C)C)C(C)C
Properties
C9H21N
Molar mass 143.274 g·mol−1
Appearance Colorless liquid
Odor Ichtyal, ammoniacal
Density 0.752 g/cm3
Boiling point 131.8 °C (269.2 °F; 404.9 K) 47°C at 1.9 kPa
Related compounds
Related amines
Related compounds
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
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Infobox references

StructureEdit

Triisopropylamine is notable as being among the most sterically hindered amines currently known. The even more crowded tri-tert-butylamine (tBu3N) has never been synthesized, although ab initio quantum chemical computations as well as the existence of the even more crowded 2,2,4,4-tetramethyl-3-t-butyl-pentane-3-ol (tri-tert-butylcarbinol, tBu3COH) implies that it should be a stable molecule if it could be prepared. To date, di-tert-butyl(isopropyl)amine (tBu2iPrN) has been prepared in low yield, as have a handful of tri-tert-alkylamines in which two of the tert-alkyl groups are tied together in a ring, but the authors of a 2018 study predict that tBu3N will likely remain a longstanding unsolved synthetic challenge.[3]

In the early 1990s, theoretical studies and electron diffraction analysis of the 3D structure of the molecule, in the gas phase or in non-polar solvents, indicated that the bonds between the nitrogen atom and the three carbon atoms were nearly coplanar in the ground state, instead of forming a trigonal pyramid as in simpler amines.[4][5] The average C-N-C angle was claimed to be 119.2°,[2] much closer to the 120° of the flat configuration than to the 111.8° of trimethylamine. This peculiarity was attributed to steric hindrance by the bulky isopropyl radicals. However, in 1998 X-ray diffraction analysis of the crystallized solid showed that the C3N core is actually pyramidal, with the N atom lying approximately 0.28 Å off the carbons' plane (whereas in trimethylamine the distance is about 0.45 Å). However the researchers could not rule out the crystal field effect as the cause of the asymmetry.[6]

The C-C-C planes of the isopropyl groups are slightly tilted (about 5°) relative to the threefold symmetry axis of the C3N core.[4][6][7]

PreparationEdit

Steric effects make triisopropylamine difficult to synthesise and unlike less hindered tertiary amines (such as triethylamine) it cannot be produced by the alkylation of ammonia with alcohol; attempts to do so stall at diisopropylamine. It can be prepared from diisopropylamine on the laboratory scale:[2]

 

Industrial synthesis involves the reaction of ammonia with propylene oxide followed by hydrogenation.[8]

See alsoEdit

ReferencesEdit

  1. ^ G. Graner, E. Hirota, T. Iijima, K. Kuchitsu, D. A. Ramsay, J. Vogt and N. Vogt (2003), C9H21N, Triisopropylamine. In Molecules Containing Five or More Carbon Atoms, volume 25D of the series Landolt-Börnstein - Group II Molecules and Radicals. Springer-Verlag. ISBN 978-3-540-42860-2; DOI 10.1007/10735542_789.
  2. ^ a b c Hans Bock; Ilka Goebel; Zdenek Havlas; Siegfried Liedle; Heinz Oberhammer (1991). "Triisopropylamine: A Sterically Overcrowded Molecule with a Flattened NC3 Pyramid and a "p-Type" Nitrogen Electron Pair". Angew. Chem. Int. Ed. 30 (2): 187–190. doi:10.1002/anie.199101871.
  3. ^ Banert, Klaus; Heck, Manuel; Ihle, Andreas; Kronawitt, Julia; Pester, Tom; Shoker, Tharallah (2018-05-04). "Steric Hindrance Underestimated: It is a Long, Long Way to Tri- tert -alkylamines". The Journal of Organic Chemistry. 83 (9): 5138–5148. doi:10.1021/acs.joc.8b00496. ISSN 0022-3263.
  4. ^ a b Arthur M. Halpern; B. R. Ramachandran (1992). "Photophysics of a sterically crowded tertiary-saturated amine: triisopropylamine". J. Phys. Chem. 96 (24): 9832–9839. doi:10.1021/j100203a047.
  5. ^ Christoph Kölmel, Christian Ochsenfeld & Reinhart Ahlrichs (1992). "An ab initio investigation of structure and inversion barrier of triisopropylamine and related amines and phosphines". Theoretical Chemistry Accounts: Theory, Computation, and Modeling (Theoretica Chimica Acta). 82 (3–4).
  6. ^ a b Boese, R.; Bläser, D.; Antipin, M. Y.; Chaplinski, V.; de Meijere, A. (1998). "Non-planar structures of Et3N and Pri3N: a contradiction between the X-ray, and NMR and electron diffraction data for Pri3N". Chem. Commun. (7): 781–782. doi:10.1039/a708399h.
  7. ^ Yang M, Albrecht-Schmitt T, Cammarata V, Livant P, Makhanu DS, Sykora R, Zhu W (2009). "Trialkylamines more planar at nitrogen than triisopropylamine in the solid state". J. Org. Chem. 74 (7): 2671–8. doi:10.1021/jo802086h. PMID 19323571.
  8. ^ Sk A3 932005, "Wasteless process for preparing triisopropanolamine", issued Dec 5, 2008, assigned to Novacke Chemicke Zavody