Selective Synthesis of Carbonates from Glycerol, CO2, and Alkyl Halides Using tert-Butyltetramethylguanidine

Masatoshi Mihara; Kaname Moroga; Tetsuo Iwasawa; Takeo Nakai; Takatoshi Ito; Toshinobu Ohno; Takumi Mizuno

doi:10.1055/s-0037-1610027

Synlett, Table of Contents

Synlett 2018; 29(13): 1759-1764
DOI: 10.1055/s-0037-1610027

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Selective Synthesis of Carbonates from Glycerol, CO₂, and Alkyl Halides Using tert-Butyltetramethylguanidine

Masatoshi Mihara*

^aOsaka Research Institute of Industrial Science and Technology, 1-6-50 Morinomiya, Joto-ku, Osaka 536-8553, Japan Email: mihara@omtri.or.jp

,

Kaname Moroga

^bFaculty of Science and Technology, Ryukoku University, Otsu, Shiga 520-2194, Japan

,

Tetsuo Iwasawa

^bFaculty of Science and Technology, Ryukoku University, Otsu, Shiga 520-2194, Japan

,

Takeo Nakai

^aOsaka Research Institute of Industrial Science and Technology, 1-6-50 Morinomiya, Joto-ku, Osaka 536-8553, Japan Email: mihara@omtri.or.jp

,

Takatoshi Ito

^aOsaka Research Institute of Industrial Science and Technology, 1-6-50 Morinomiya, Joto-ku, Osaka 536-8553, Japan Email: mihara@omtri.or.jp

,

Toshinobu Ohno

^aOsaka Research Institute of Industrial Science and Technology, 1-6-50 Morinomiya, Joto-ku, Osaka 536-8553, Japan Email: mihara@omtri.or.jp

,

Takumi Mizuno

^aOsaka Research Institute of Industrial Science and Technology, 1-6-50 Morinomiya, Joto-ku, Osaka 536-8553, Japan Email: mihara@omtri.or.jp

› Author Affiliations

Abstract

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Abstract

Herein, we describe the guanidine-promoted synthesis of carbonates from glycerol, CO₂, and alkyl halides. Specifically, a linear tricarbonate (1,2,3-tri-O-butoxycarbonylglycerol), a dicarbonate [butyl (2-oxo-1,3-dioxolan-4-yl)methyl carbonate] containing a linear and a cyclic moiety, and a cyclic monocarbonate (4-hydroxymethyl-2-oxo-1,3-dioxolan) were selectively obtained in good yields, which were strongly affected by the steric bulkiness of the guanidine group substituents. The developed method exhibits the advantages of high efficiency and mild conditions, thus being a powerful tool for the synthesis of value-added products from industrial by-products.

Key words

carbon dioxide - glycerol - carbonates - guanidines

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References

References and Notes

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13 General Procedure for the Synthesis of Linear Tricarbonates 1 Using Base B A stainless steel autoclave was charged with glycerol (1 mmol), base B (6 mmol), and NMP (1 mL), flushed three times with CO₂, and finally charged with CO₂ to 0.7 MPa at room temperature. The obtained mixture was magnetically stirred at 25 °C for 1 h, and an alkyl halide (10 mmol) was added at room temperature after CO₂ evacuation, followed by repeated CO₂ flushing/charging to 0.7 MPa. The reaction mixture was magnetically stirred at 25 °C for 18 h under 0.7 MPa pressure of CO₂. After EtOAc was added to the resulting mixture to precipitate the dissolved salt, the salt was removed with a Buchner funnel and washed with EtOAc. The combined filtrate was concentrated in vacuo, and the obtained product ratios were determined by ¹H NMR spectroscopic measurements. The crude product was purified by silica gel column chromatography, affording linear tricarbonates 1. 1,2,3-Tri-O-(2-butynyloxy)carbonylglycerol (1j) IR (neat): 2959, 2924, 2323, 2241, 1756, 1442, 1384, 1237, 1156, 961, 923, 789 cm^–1. ¹H NMR (600 MHz, CDCl₃): δ = 1.87 (t, J = 2.4 Hz, 9 H), 4.32 (dd, J = 12.0, 6.0 Hz, 2 H), 4.44 (dd, J = 12.0, 4.8 Hz, 2 H), 4.70–4.73 (m, 6 H), 5.12–5.15 (m, 1 H) ppm. ¹³C NMR (151 MHz, CDCl₃): δ = 3.59, 56.61, 56.72, 65.26, 72.12, 72.20, 72.71, 84.45, 84.54, 153.74, 154.16 ppm. HRMS (ESI): m/z calcd for C₁₈H₂₀NaO₉ [M + Na]⁺: 403.1005; found: 403.1004.
14 General Procedure for the Synthesis of Cyclic Carbonates (2a and 3) Using Base B Glycerol (1 mmol), base B (2 or 6 mmol), and NMP (1 mL) were added to a glass vessel connected to an injection port equipped with a three-way cock. The vessel was charged with CO₂ from a balloon, and it was stirred at 25 °C for 1 h. An alkyl bromide (2 or 6 mmol) was added dropwise at 50 °C for 3 h under 0.1 MPa of CO₂ pressure and further stirred for another 1 h. The workup and purification were the same as those reported in the general procedure for the synthesis of compound 1. 2-Butynyl (2-oxo-1,3-dioxolan-4-yl)methyl carbonate (2j) IR (neat): 2960, 2925, 2322, 2241, 1798, 1758, 1394, 1267, 1170, 1088, 1053, 951, 789, 772 cm^–1. ¹H NMR (600 MHz, CDCl₃): δ = 1.87 (t, 1.8 Hz, 3 H), 4.33 (dd, J = 12.6, 4.2 Hz, 1 H), 4.36 (dd, J = 9.0, 6.6 Hz, 1 H), 4.45 (dd, J = 12.6, 4.2 Hz, 1 H), 4.57 (t, J = 9.0 Hz, 1 H), 4.73 (q, J = 1.8 Hz, 2 H), 4.92–4.96 (m, 1 H) ppm. ¹³C NMR (151 MHz, CDCl₃): δ = 3.63, 56.98, 65.71, 66.09, 71.96, 73.24, 84.83, 154.05, 154.13 ppm. HRMS (ESI): m/z calcd for C₉H₁₀NaO₆ [M + Na]⁺: 237.0375; found: 237.0368.
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