Synthesis and Properties of 1,2,3-Triethoxypropane: A Glycerol-Derived Green Solvent Candidate

Abstract

Etherification with high selectivity and yield has been one of the challenges for expanding the realm of glycerol transformations. In this work, a small glycerol triether molecule, 1,2,3-triethoxypropane (1,2,3-TEP, CAS 162614-45-1), was designed and synthesized through a two-step strategy using epichlorohydrin as the starting material with ethanol and bromoethane as etherification reagents. The overall yield (after rigorous distillation) was 43.9%, higher than those of methods previously published in the literature. Thermophysical properties for 1,2,3-TEP are herein reported for the first time. Densities and viscosities measured at 1 atm from 20 to 80 °C show that 1,2,3-TEP is a less dense and less viscous liquid than glycerol and the corresponding 1,3-diether intermediate, 1,3-diethoxypropan-2-ol (1,3-DEP, CAS #4043-59-8). CO 2 solubility in 1,2,3-TEP was investigated under pressures of 2−8 atm at 30, 45, 60, and 75 °C with respective K H values of 46.2, 57.4, 69.4, and 81.7 atm, enabling reliable predictions on CO 2 solubility within this range of temperature and pressure conditions. Comparison of Henry's law constants and vapor pressure between 1,2,3-TEP and diglyme from 0 to 75 °C has indicated its potential as an alternative CO 2 capture solvent to those used in the Selexol process. 1,2,3-TEP showed broad miscibility with common solvents except water. The dipole moment of the minimum energy structure in the gas phase is calculated to be 1.47 D, but this value increases to 2.5−2.7 D in common solvents. The data obtained in this work are meaningful in guiding the further synthesis of a series of glycerol triether derivatives and developing uses for 1,2,3-TEP and related compounds.

Glycerol‐derived solvents containing two or three distinct functional groups enabled by trifluoroethyl glycidyl ether

“…Considering these miscibility data with those from our previous works on symmetric compounds, 38,48,52 they present a broad range of solvent candidates from which to choose depending on the requirements of hydrophilcity/phobicity and oleophilicity/phobicity. Table 10 shows that the oleophilicity and hydrophilicity for glycerol derivatives, including diether alcohols, diether ketones, and triethers, can be adjusted by the selection of functional groups except a triether that simultaneously exhibits both oleophobic and hydrophobic properties.…”

“…and [ME, ME, F] were calculated as À10.0, À11.1, À11.0, À11.1 and À11.9 kJÁmol À1 , respectively, which are indicative of a "physical solvent" (À8 kJÁmol À1 to À15 kJÁmol À1 ). 13,[52][53][54] The magnitude of H CO2 was predicted in a consecutive way using the parameters in Table 7 extrapolating to a range from 273.15 to 353.15 K in Figure 5. DMPEG, one of the most popular industrial gas removal solvent, and two of its oligomers (diglyme and triglyme) 55 were chosen for comparison.…”

Benchmarking Semiempirical QM Methods for Calculating the Dipole Moment of Organic Molecules

“…For example, strong dipole–dipole interactions can rationalize strong intermolecular interactions that lead to higher melting and boiling points . The dipole moment can also be used as a descriptor for designing solvents. − Molecules with large dipole moments readily polarize other molecules and promote dipole–dipole or dipole-induced dipole interactions that help miscibility and solubility. In addition, the dipole moment is also critical to understanding photon absorption-induced transitions in rotational and vibrational spectroscopy to name a few applications.…”

Properties of Imidazolium Ionic Liquids with Glycerol-Derived Functional Groups

“…Among many versatile applications, the relatively high affinity of ILs to specific gases has been revealed. − As etherification and fluorination have already been proven of to be effective strategies to enhance CO 2 solubility, , the CO 2 absorption performance of [(ME,F)-mim]­[Tf 2 N] was evaluated in this work at 303.15, 318.15, 333.15, and 348.15 K under moderate pressures (0.2–1.0 MPa) as a representative of etherified and fluorinated ILs we have developed. The CO 2 partial pressure, along with corresponding CO 2 molar ratio calculated based on data collected at each equilibrium of absorption, is shown in Table .…”