Direct synthesis of bio-based alkyl and furanic diol ethers, acetates, ether-acetates, and carbonates

Patent metadata

Field	Value
Publication number	US-9890131-B2
Application number	US-201415102298-A
Country	US
Kind code	B2
Filing date	Dec 19, 2014
Priority date	Dec 20, 2013
Publication date	Feb 13, 2018
Grant date	Feb 13, 2018

Abstract

A method of preparing a glycol mono-ether or mono-acetate, or carbonate involving either one of two pathways from alkylene glycols, HMF or its reduction derivative products (i.e., FDM, bHMTHFs), is provided. In particular, according to one pathway, the alkylene glycol, HMF or FDM, bHMTHFs are reacted with a dialkyl carbonate in the presence of a deprotonating agent, in substantial absence of an extrinsic catalyst, to produce an ether, and subsequently reacting the ether with an acid base. According to the other pathway, alkylene glycols are reacted with an acetate donor in the presence of an acid, base, to generate an alkylene mono-acetate, and etherified with a carbonate in the presence of a deprotonating agent.

First claim

We claim:

1. A method of preparing a mono-ester-ether from a linear or mono-cyclic diol compound, comprising either a first pathway or second pathway, wherein:
in the first pathway, a diol compound selected from the group consisting of ethylene glycol (EG), propylene glycol (PG), 2,3 butane diol (BDO), furandimethanol and tetrahydrofuran dimethanol is contacted with an R 1 organic acid of the formula R 1 —CO 2 H wherein R 1 is a C 1 to C 8 alkyl, cycloalkyl or aromatic moiety in the presence of a Brønsted acid at a temperature and for time sufficient to form a R 1 mono ester of the diol compound, then the R 1 mono ester of the diol compound is contacted with a R 2 alkyl diester of the formula R 2 (CO 3 )R 2 in which R 2 is a C 1 to C 8 alkyl moiety in the presence of a deprotonating agent at a temperature and for a time sufficient to form the monoester ether; or
in the second pathway, a diol compound selected from the group consisting of ethylene glycol (EG), propylene glycol (PG), 2,3 butane diol (BDO), furandimethanol and tetrahydrofuran dimethanol is contacted with the an R 2 alkyl diester of the formula R 2 (CO 3 )R 2 in which R 2 is a C1 to C8 alkyl moiety in the presence of a deprotonating agent at a temperature and for a time sufficient to form a mono ether of the diol compound, then the mono ether of the diol compound is contacted with an R 1 organic acid of the formula R 1 —CO 2 H wherein R 1 is a C 1 to C 8 alkyl, cycloalkyl or aromatic moiety in the presence of a Brønsted acid at a temperature and for time sufficient to form the monoester ether.

2. The method according to claim 1 , wherein said R 1 organic acid is acetic acid and said mono-ester-ether is an ether acetate compound.

3. The method according to claim 1 , wherein said deprotonating agent is a Brønsted base.

4. The method according to claim 1 , wherein said deprotonating agent is selected from the group consisting of potassium carbonate, sodium carbonate, calcium carbonate, and an amine.

5. The method according to claim 1 , wherein said temperature for contacting with the Brønsted acid and with the deprotonating agent is at a temperature between about 70° C. and 150° C.

6. The method according to claim 1 , wherein said temperature for contacting with the Brønsted acid and with the deprotonating agent is at a temperature between about 80° C. and 130° C.

7. The method according to claim 1 wherein said temperature for contacting with the Brønsted acid and with the deprotonating agent is at a temperature between about 90° C. to about 120° C.

8. The method according to claim 1 , wherein said deprotonating agent is an inorganic carbonate present in an amount of at least one (1) to about three (3) stoichiometric equivalents per diol compound.

Assignees

• Archer Daniels Midland Co

Inventors

• Stensrud Kenneth
• Venkitasubramanian Padmesh

Classifications

• C07C67/343

  by increase in the number of carbon atoms · CPC title

• C07D493/04 Primary

  Ortho-condensed systems · CPC title

• C07D307/12

  Radicals substituted by oxygen atoms · CPC title

• C07D307/42 Primary

  Singly bound oxygen atoms · CPC title

• C07C68/06

  from organic carbonates · CPC title