585-48-8 Usage
Overview
2,6-Di-tert-butylpyridine is a weak base used in the preparation of 2, 6-di-tert-butylpyridine hydrotriflate. It is used as a proton scavenger to check the progress of the living polymerization of isobutylene. It is associated with cerric ammonium nitrate and used in the alfa-enolation of aldehydes. It is involved in the preparation of vinyl triflate using polymer-bound 2,6-di-tert-butylpyridine. Since it was first synthesized by Brown and Kanner[1], 2,6-di-tert-butylpyridine has attracted the interest of many researchers because of its unusually low basicity: with its two-alkyl substituents, DTBP is nevertheless a weaker base than unsubstituted pyridine in aqueous solution. Brown and Kanner[1] and others[2] proposed that the abnormally low basicity of DTBP was caused by steric hindrance to hydration of DTBPH+. Recent determinations of gas-phase proton affinities of DTBP and other alkyl-substituted pyridines showed that the basicity of DTBP in the gas phase was normal[2, 3], which confirmed that its weak basicity in water was due to solvent effects on DTBP and (or) DTBPH+. A complete analysis of the thermodynamic cycles linking the protonation processes of DTBP and other pyridines in the gas phase and in aqueous solution led Arnett and Chawla[2] to conclude that there was indeed some hindrance to the hydration of DTBPH+ as reflected in its abnormally low enthalpy of hydration. However, more recently Hopkins et al.[3], after investigating the protonation of additional tertbutylpyridines and repeating the thermodynamic determinations of Amett and Chawla[2] of DTBP, concluded from their new data that the hydration enthalpy of DTBPH+ was normal but that the corresponding entropy was abnormal; they suggested that the rotation of the water molecule attached to DTBPH+ and of -CMe3 was restricted. These results and conclusions were in agreement with the gas phase studies of Moet-Ner and Sieck[4] on the attachment of one water molecule to a series of pyridinium cations including DTBPH+.
Reference
H. C. BROWN and B. KANNERJ. Am. Chem. Soc. 75, 3865 (1953).
E. M. ARNETT and B. CHAWLAJ. Am. Chem. Soc. 101, 7141 (1979).
H.P.HOPKINSD,.V.JAHAGIRDAP.RS,.MOULIKD,.H.AUE, H. M. WEBB,W. R. DAVIDSON and M. D. PEDLEY. J.. Am. Chem. Soc. 106,4341 (1984).
M. MEOT-NEaRnd L. W. SIECK J. Am. Chem. Soc. 105, 2956 (1983)
Chemical Properties
dark brown liquid
Uses
Different sources of media describe the Uses of 585-48-8 differently. You can refer to the following data:
1. 2,6-Di-tert-butylpyridine is used in the preparation of 2, 6-di-tert-butylpyridine hydrotriflate. It is used as a proton scavenger to check the progress of the living polymerization of isobutylene. It is associated with cerric ammonium nitrate and used in the alfa-enolation of aldehydes. It is involved in the preparation of vinyl triflate using polymer-bound 2,6-di-tert-butylpyridine.
2. 2,6-Di-tert-butylpyridine was used as proton trapping agent to investigate the living polymerization of isobutylene. It was also used with cerric ammonium nitrate in the α-enolation of aldehydes leading to 1,4-dicarbonyl systems.
General Description
Reactivity of 2,6-di-tert-butylpyridine with iron(III) tetraphenylporphyrin pi-cation radical has been examined by proton NMR spectroscopy. Reaction of 2,6-di-tert-butylpyridine with methyl iodide and methyl fluorosulfonate under high pressure has been reported.
Purification Methods
Redistil it from KOH pellets. [Beilstein 20 III/IV 2868.]
Check Digit Verification of cas no
The CAS Registry Mumber 585-48-8 includes 6 digits separated into 3 groups by hyphens. The first part of the number,starting from the left, has 3 digits, 5,8 and 5 respectively; the second part has 2 digits, 4 and 8 respectively.
Calculate Digit Verification of CAS Registry Number 585-48:
(5*5)+(4*8)+(3*5)+(2*4)+(1*8)=88
88 % 10 = 8
So 585-48-8 is a valid CAS Registry Number.
InChI:InChI=1/C13H21N/c1-12(2,3)10-8-7-9-11(14-10)13(4,5)6/h7-9H,1-6H3
585-48-8Relevant articles and documents
Examining the Effects of Monomer and Catalyst Structure on the Mechanism of Ruthenium-Catalyzed Ring-Opening Metathesis Polymerization
Wolf, William J.,Lin, Tzu-Pin,Grubbs, Robert H.
supporting information, p. 17796 - 17808 (2019/11/11)
The mechanism of Ru-catalyzed ring-opening metathesis polymerization (ROMP) is studied in detail using a pair of third generation ruthenium catalysts with varying sterics of the N-heterocyclic carbene (NHC) ligand. Experimental evidence for polymer chelation to the Ru center is presented in support of a monomer-dependent mechanism for polymerization of norbornene monomers using these fast-initiating catalysts. A series of kinetic experiments, including rate measurements for ROMP, rate measurements for initiation, monomer-dependent kinetic isotope effects, and activation parameters were useful for distinguishing chelating and nonchelating monomers and determining the effect of chelation on the polymerization mechanism. The formation of a chelated metallacycle is enforced by both the steric bulk of the NHC and by the geometry of the monomer, leading to a ground-state stabilization that slows the rate of polymerization and also alters the reactivity of the propagating Ru center toward different monomers in copolymerizations. The results presented here add to the body of mechanistic work for olefin metathesis and may inform the continued design of catalysts for ROMP to access new polymer architectures and materials.
The effect of temperature, catalyst and sterics on the rate of N-heterocycle dehydrogenation for hydrogen storage
Dean, Darrell,Davis, Boyd,Jessop, Philip G.
body text, p. 417 - 422 (2011/04/21)
Efficient hydrogen storage is one of the critical requirements for the use of hydrogen fuel cells in light-duty vehicles. Our investigation of reversible chemical hydrogen storage systems has led to the development of a mixed endothermic-exothermic carrier system. Herein we further investigate the factors affecting the dehydrogenation rate of these carriers. A range of heterogeneous catalysts was synthesized via sol-gel methodology and their activity for indoline dehydrogenation was assessed. Metals used included Fe, Co, Ni, Cu, Ru, Rh, Pd, Ir and Pt. SiO2, Al2O3, TiO2 and ZrO2 were used as supports and Pd/SiO2 gave the highest conversion over a fixed time. A marked increase in the rate of indoline dehydrogenation was observed when the temperature was increased between 100 and 180 °C, with measured first order rate constants of 1.8 × 10 -4 s-1 at 100 °C and 5.9 × 10-4 at 120 °C. Although piperidines dehydrogenate more slowly than indolines, steric hindrance around the nitrogen atom in piperidine increases its dehydrogenation rate significantly.
