2,4,6-Tri(propan-2-ylidene)-1,3,5-trioxane

2,4,6-Tri(propan-2-ylidene)-1,3,5-trioxane

1,3,5-Trioxane-2,4,6-trione (cyclic trimer of CO₂) is the product of a four-step synthesis: chlorination of isobutyraldehyde; cyclotrimerization of 2-chloro-2-methylpropanal; dehydochlorination of 2,4,6-tris(2-chloropropan)-2-yl-1,3,5-trioxane; ozonolysis at −80 °C of 2,4,6-tri(propan-2-ylidene)-1,3,5-trioxane. This trioxane-trione is detected in solution at temperatures between −80 to −40 °C, and its conversion to CO₂ is monitored by ¹³C NMR and FTIR. The CO₂ trimer has a half-life of approximately 40 min at −40 °C.

As a product of combustion and respiration whose accumulation in the atmosphere has become a cause for significant concern, carbon dioxide has been the subject of much research directed at its reutilization. Various approaches toward this CO₂ reutilization goal have been described in excellent reviews over the past two decades.Important processes involve reduction with hydrogen,coupling with other small molecules, incorporation into polymers and artificial photosynthesis. The main products include fuels, solvents, chemical intermediates and polymers.

The efficiency of these commercial processes in terms of reagent usage is relatively low with respect to the fraction of CO₂ incorporated into the product; the highest being for urea (57%), and decreasing for salicylic acid (36%) and methanol (10%). This could be raised to 100% if a CO₂ self-fixation chemistry could be developed. Ideally with a sufficient input of energy, CO₂ would react with itself to yield a liquid or solid product from which this energy could be extracted when needed for useful work. Such chemistry has been the subject of theoretical calculation for structures representing the linear polymer and cyclic oligomers of CO₂.

With respect to thermodynamic stability, the cyclic trimer has been described as “feasible” although energetically less stable than three CO₂ molecules by 27 kJ/mol per CO₂ unit.(10)Regarding kinetic stability of the cyclic trimer toward fragmentation to CO₂, calculated barriers for this decomposition have ranged from activation energies of 61 to 172 kJ/mol depending on the computational method with calculated half-lives ranging from days to milliseconds at ambient conditions and substantially longer at lower temperatures.

 The cyclic trimer of CO₂has also been proposed as a low-energy intermediate in the transformation of CO₂ to an extended solid.

The formation of an orthocarbonate extended covalent structure of interconnected six-membered rings was predicted by model calculation with the finding of a stabilization energy that increased with molecular size. Later experimental work found under extreme pressure/temperature (40 GPa/1800 K), CO₂ will transform to a metastable extended solid which has been characterized as a Phase V form of CO₂ with a sigma bonded quartz-like structure.

 It has also been proposed that sorption of CO₂ into the isolated nanoscale confined spaces of sulfur- or nitrogen-treated porous carbon at 30 bar pressure can produce a polymeric structure of carbon dioxide as has been reported for other molecules in nanoconfined spaces.

The 1,3,5-trioxane-2,4,6-trione structure of the CO₂ cyclic trimer, 1, may represent an important intermediate or product in the self-fixation of gaseous CO₂. Theoretical studies on this molecule have indicated a possibility of kinetic stability at room temperature and as well as a possibility for it to be thermodynamically feasible.To date, no experimental evidence has been reported for its existence. The objective of this work is to synthesize compound 1 and to make an assessment of its stability. The approach is that of a model compound synthesis where the trioxane ring is first generated from substituted aldehydes and then the peripheral carbonyl structures are incorporated at low temperature in the final step. As will be shown, compound 1does not possess the stability for facile isolation and storage

Synthesis and Low Temperature Spectroscopic Observation of 1,3,5-Trioxane-2,4,6-Trione: The Cyclic Trimer of Carbon Dioxide

Michael J. Rodig^†, Arthur W. Snow^*†, Paul Scholl^§, and Simon Rea^§

^† Chemistry Division, Naval Research Laboratory, Washington, D. C. 20375, United States

^§Mettler-Toledo AutoChem, Inc., Columbia, Maryland 21046, United States

J. Org. Chem., Article ASAP

DOI: 10.1021/acs.joc.6b00647

*E-mail: arthur.snow@nrl.navy.mil.

http://pubs.acs.org/doi/full/10.1021/acs.joc.6b00647

ACS Editors' Choice - This is an open access article published under an ACS AuthorChoice License, which permits copying and redistribution of the article or any adaptations for non-commercial purposes.

 

2,4,6-Tri(propan-2-ylidene)-1,3,5-trioxane (2a)

crude product was purified by vacuum distillation (10 mmHg at 185 °C) to yield the title compound as a colorless liquid (2.32 g, 71%). ¹H NMR (CDCl₃, 300 MHz) δ = 1.63 (s, 18 H,) ppm; ¹³C NMR (CDCl₃, 75 MHz) δ = 15.0, 86.9, 144.7 ppm; IR ν_max (liquid) 2991, 2919, 2863, 1726, 1284, 1212 cm^–1; UV (CH₃CN) λ_max = 210 nm (ε = 1.57 × 10⁴ L/mol·cm); HRMS (ESI) m/z calcd for C₁₂H₁₈O₃ [M + H]⁺ 211.1334, found 211.1342. Anal. Calcd for C₁₂H₁₈O₃: C, 68.54; H, 8.68; O, 22.83. Found: C, 68.48; H; 8.76.

/////////Synthesis, Low Temperature,  Spectroscopic Observation, of 1,3,5-Trioxane-2,4,6-Trione,  The Cyclic Trimer,  Carbon Dioxide

• Supporting Info
• http://pubs.acs.org/doi/suppl/10.1021/acs.joc.6b00647

///////////// 


 Torkham, PAKISTAN,  AFGHANISTAN ,  BORDER 

Torkham

Torkham is one of the major border crossings between Afghanistan and Pakistan, located on the Torkham international border. It connects Nangarhar province of Afghanistan with Pakistan's Federally Administered Tribal Areas and Khyber Pakhtunkhwa. Wikipedia

Torkham
تورخم

Khyber Pass gate at Torkham, Pakistan

 
 

 
 
 

 
 
 

 

 

 

 

 






 


 

//////////