Method of making a multi-ring disalicylate compound

Abstract

A method of making a multi-ring disalicylate compound is disclosed. The method comprises: providing a first reagent mixture including a multi-ring aromatic alcohol, a base, and optionally a first solvent in a reactor volume; reacting the multi-ring aromatic alcohol and the base to form a first intermediate mixture comprising a salt of the multi-ring aromatic alcohol, water, and the optional first solvent; adding a second solvent to the reactor volume and removing at least partially the water and the optional first solvent from the reactor volume; adding CO2 to the reactor volume; and reacting the salt of the multi-ring aromatic alcohol and the CO2 to form a final product mixture comprising a multi-ring disalicylate compound. Other methods for making a multi-ring disalicylate compound as well as a salt of the multi-ring disalicylate compound are also disclosed.

Description

METHOD OF MAKING A MULTI-RING DISALICYLATE COMPOUND Cross-Reference to Related Application

[0001] The present application claims filing benefit of US Provisional Patent Application No. 63 / 600,068 having a filing date of November 17, 2023, US Provisional Patent Application No. 63 / 559,474 having a filing date of February 29, 2024, and US Provisional Patent Application No. 63 / 686,270 having a filing date of August 23, 2024, all of which are Incorporated herein by reference in their entirety.Background

[0002] Multi-ring disalicylate compounds have many applications. For instance, metal organic framework materials may include multi-ring disalicylate compounds for various applications, such as separations, gas storage, and / or catalysis. As one example, these metal organic framework materials and compounds may be used for selective adsorption of CO2 and / or other components, particularly due to their high CO2 adsorption properties. In addition to these applications, multi-ring disalicylate compounds may also be utilized in preparing aromatic polyesters having certain desired thermal and / or mechanical properties.

[0003] However, current methods for making certain multi-ring disalicylate compounds may not be as desirable. For instance, certain methods may be relatively expensive. Such expenses may be due to complex operations and / or the high cost of starting materials as reagents. Alternatively or in addition, certain methods may be difficult to scale up for mass production. In addition, certain methods may require relatively high temperatures and / or high pressures.

[0004] In this regard, there is a desire to provide an improved method for making multi-ring disalicylate compounds.Summary

[0005] In accordance with one embodiment of the present disclosure, a method of making a multi-ring disalicylate compound is disclosed. The method comprises: providing a first reagent mixture including a multi-ring aromatic alcohol, a base, and optionally a first solvent in a reactor volume; reacting the multi-ring aromatic alcohol and the base to form a first intermediate mixture comprising a salt of the multi-ring aromatic alcohol, water, and the optional first solvent; adding a second solvent to the reactor volume and removing at least partially the water and the optional first solvent from the reactor volume; adding CO2 to the reactorvolume; and reacting the salt of the multi-ring aromatic alcohol and the CO2 to form a final product mixture comprising the multi-ring disalicylate compound.

[0006] In accordance with another embodiment of the present disclosure, a method of making a multi-ring disalicylate compound is disclosed. The method comprises: providing a first reagent mixture including a multi-ring aromatic alcohol, a base, and optionally a first solvent in a reactor volume; reacting the multi-ring aromatic alcohol and the base to form a first intermediate mixture comprising a salt of the multi-ring aromatic alcohol, water, and the optional first solvent; adding a second solvent comprising a non-cyclic ether to the reactor volume to form a second intermediate mixture; adding CO2 to the reactor volume; and reacting the salt of the multi-ring aromatic alcohol and the CO2 to form a final product mixture comprising the multi-ring disalicylate compound.

[0007] In accordance with another embodiment of the present disclosure, a method of making a multi-ring disalicylate compound is disclosed. The method comprises: providing a second reagent mixture including a salt of a multi-ring aromatic alcohol and a second solvent comprising a non-cyclic ether in a reactor volume; adding CO2 to the reactor volume; and reacting the salt of the multi-ring aromatic alcohol and the CO2 to form a final product mixture comprising the multiring disalicylate compound.

[0008] In accordance with another embodiment of the present disclosure, a multi-ring disalicylate compound is disclosed. The multi-ring disalicylate compound is formed according to a method comprising: providing a first reagent mixture including a multi-ring aromatic alcohol, a base, and optionally a first solvent in a reactor volume; reacting the multi-ring aromatic alcohol and the base to form a first intermediate mixture comprising a salt of the multi-ring aromatic alcohol, water, and the optional first solvent; adding a second solvent to the reactor volume and removing at least partially the water and the optional first solvent from the reactor volume; adding CO2 to the reactor volume; and reacting the salt of the multi-ring aromatic alcohol and the CO2 to form a final product mixture comprising a multi-ring disalicylate compound.

[0009] In accordance with another embodiment of the present disclosure, a method of making a salt of a multi-ring disalicylate compound is disclosed. The method comprises: providing a first reagent mixture including a multi-ring aromaticalcohol, a base, and optionally a first solvent in a reactor volume; reacting the multi-ring aromatic alcohol and the base to form a first intermediate mixture comprising a salt of the multi-ring aromatic alcohol, water, and the optional first solvent; adding a second solvent to the reactor volume and removing at least partially the water and the optional first solvent from the reactor volume; adding CO2 to the reactor volume; and reacting the salt of the multi-ring aromatic alcohol and the CO2 to form a reaction product mixture comprising the salt of the multi-ring disalicylate compound.

[0010] In accordance with another embodiment of the present disclosure, a method of making a salt of a multi-ring disalicylate compound is disclosed. The method comprises: providing a first reagent mixture including a multi-ring aromatic alcohol, a base, and optionally a first solvent in a reactor volume; reacting the multi-ring aromatic alcohol and the base to form a first intermediate mixture comprising a salt of the multi-ring aromatic alcohol, water, and the optional first solvent; adding a second solvent comprising a non-cyclic ether, an aromatic ether, or a mixture thereof to the reactor volume to form a second intermediate mixture; adding CO2 to the reactor volume; and reacting the salt of the multi-ring aromatic alcohol and the CO2 to form a reaction product mixture comprising the salt of the multi-ring disalicylate compound.

[0011] In accordance with another embodiment of the present disclosure, a method of making a salt of a multi-ring disalicylate compound is disclosed. The method comprises: providing a second reagent mixture including a salt of a multiring aromatic alcohol and a second solvent comprising a non-cyclic ether, an aromatic ether, or a mixture thereof in a reactor volume; adding CO2 to the reactor volume; and reacting the salt of the multi-ring aromatic alcohol and the CO2 to form a reaction product mixture comprising the salt of the multi-ring disalicylate compound.

[0012] In accordance with another embodiment of the present disclosure, a method of making a multi-ring disalicylate compound is disclosed. The method comprises: providing a first reagent mixture including a multi-ring aromatic alcohol, a base, and optionally a first solvent in a reactor volume; reacting the multi-ring aromatic alcohol and the base to form a first intermediate mixture comprising a salt of the multi-ring aromatic alcohol, water, and the optional first solvent; adding asecond solvent to the reactor volume and optionally removing at least partially the water and the optional first solvent from the reactor volume; adding CO2 to the reactor volume; reacting the salt of the multi-ring aromatic alcohol and the CO2 to form a reaction product mixture comprising a salt of the multi-ring disalicylate compound and one or more impurities; contacting the reaction product mixture with an acid and a third solvent for at least partially dissolving the one or more impurities; separating the third solvent with the dissolved one or more impurities from the reaction product mixture to form a purified product mixture; and acidifying the purified product mixture to form a final product mixture comprising a multi-ring disalicylate compound.

[0013] In accordance with another embodiment of the present disclosure, a multi-ring disalicylate compound is disclosed. The multi-ring disalicylate compound is formed according to a method comprising: providing a first reagent mixture including a multi-ring aromatic alcohol, a base, and optionally a first solvent in a reactor volume; reacting the multi-ring aromatic alcohol and the base to form a first intermediate mixture comprising a salt of the multi-ring aromatic alcohol, water, and the optional first solvent; adding a second solvent to the reactor volume and optionally removing at least partially the water and the optional first solvent from the reactor volume; adding CO2 to the reactor volume; reacting the salt of the multi-ring aromatic alcohol and the CO2 to form a reaction product mixture comprising a salt of the multi-ring disalicylate compound and one or more impurities; contacting the reaction product mixture with an acid and a third solvent for at least partially dissolving the one or more impurities; separating the third solvent with the dissolved one or more impurities from the reaction product mixture to form a purified product mixture; and acidifying the purified product mixture to form a final product mixture comprising the multi-ring disalicylate compound.

[0014] In accordance with another embodiment of the present disclosure, a multi-ring disalicylate compound is disclosed. The multi-ring disalicylate compound is formed according to any of the aforementioned methods of making a multi-ring disalicylate compound.

[0015] In accordance with another embodiment of the present disclosure, a metal organic framework is disclosed. The metal organic framework is formed from any of the aforementioned multi-ring disalicylate compounds.Brief Description of the Drawings

[0016] Figure 1 illustrates one reaction scheme in accordance with the present disclosure.

[0017] Figures 2 and 3 provide HPLC spectra of the product mixture based on Example 1 and a standard.

[0018] Figures 4 and 5 provide reaction information of Example 3.

[0019] Figure 6 provides an HPLC spectrum of the product mixture based on Example 3.Detailed Description

[0020] It is to be understood by one of ordinary skill in the art that the present discussion is a description of exemplary embodiments only and is not intended as limiting the broader aspects of the present disclosure.

[0021] Generally speaking, the present disclosure is directed to a method of making a multi-ring disalicylate compound. As indicated herein, various synthesis routes may be utilized to make the multi-ring disalicylate compound or a salt of the multi-ring disalicylate compound.

[0022] For instance, in one embodiment, as mentioned herein, the process may include a step of removing at least partially water present in a reactor volume, such as prior to formation of or completion of the reaction step of forming the multiring disalicylate compound and / or a salt of the multi-ring disalicylate compound. Such water removed may have been formed in-situ during the reaction.

[0023] In another embodiment, as mentioned herein, the method may utilize a particular solvent, particularly during the carboxylation reaction with CO2. Such solvent may comprise a non-cyclic ether, an aromatic ether, or a mixture thereof.

[0024] Related, in a further embodiment, rather than beginning the reaction with the multi-ring aromatic alcohol, the reaction may begin with a salt of the multiring aromatic alcohol, such as an alkali salt, in particular a dialkali salt, of the multiring aromatic alcohol. In this regard, during the carboxylation reaction with CO2, the reaction may be conducted using a solvent comprising a non-cyclic ether, an aromatic ether, or a mixture thereof.

[0025] Related, in another further embodiment, rather than beginning the reaction with the multi-ring aromatic alcohol or a salt of the multi-ring aromatic alcohol, the reaction may begin with a salt, such as an alkali salt, in particular adialkali salt, of the multi-ring disalicylate compound. In this regard, the salt of the multi-ring disalicylate compound may be acidified as disclosed herein for forming the multi-ring disalicylate compound.

[0026] In a further embodiment, the method may utilize selective dissolution for purification. For instance, a particular solvent may be utilized to dissolve one or more impurities, such as the multi-ring aromatic alcohol wherein such solvent may be considered a poor solvent for the multi-ring disalicylate compound or the salt of the multi-ring disalicylate compound.

[0027] The present inventors have discovered that by utilizing the methods as disclosed herein, a desired reaction may be realized for forming the multi-ring disalicylate compound.

[0028] In this regard, the present disclosure may be directed to a method of making a multi-ring disalicylate compound and / or a salt thereof. In one embodiment, the present disclosure may be directed to a method of making a multi-ring disalicylate compound. In another embodiment, the present disclosure may be directed to a method of making a salt of a multi-ring disalicylate compound.

[0029] In general, the method may include any combination of steps as provided below. For instance, the steps may vary depending on the starting reagents (e.g., multi-ring aromatic alcohol + base, salt of the multi-ring aromatic alcohol, or salt of a multi-ring disalicylate compound). Nevertheless, the combination or order of steps may be selected in order to proceed for one or more starting reagents to a multi-ring disalicylate compound as defined herein and / or a respective mixture as defined herein including a multi-ring disalicylate compound. Similarly, the combination or order of steps may be selected in order to proceed for one or more starting reagents to a salt of a multi-ring disalicylate compound as defined herein and / or a respective mixture as defined herein including a salt of a multi-ring disalicylate compound.

[0030] In one embodiment, the method may include a step of providing a first reagent mixture including a multi-ring aromatic alcohol and a base. The first reagent mixture may optionally include a first solvent in one embodiment. In another embodiment, the first reagent mixture may include a first solvent. By providing the first reagent mixture, it may be provided in a reactor volume. In this regard, the first reagent mixture may be provided by forming prior to providing intothe reactor volume in one embodiment. In another embodiment, the first reagent mixture may be provided by forming within the reactor volume.

[0031] In providing the first reagent mixture, if providing the reagents separately to the reactor volume, the order is not necessarily limited. For instance, in one embodiment, the base may be provided and then the multi-ring aromatic alcohol may be provided. In another embodiment, the multi-ring aromatic alcohol may first be provided and then the base may be provided. Regardless, the providing step, whether individually or collectively, may be at a temperature of about 10°C or more, such as about 12°C or more, such as about 14°C or more, such as about 16°C or more, such as about 18°C or more, such as about 20°C or more, such as about 22°C or more, such as about 24°C or more. The providing step may be at a temperature of about 60°C or less, such as about 56°C or less, such as about 52°C or less, such as about 48°C or less, such as about 44°C or less, such as about 40°C or less, such as about 36°C or less, such as about 32°C or less, such as about 28°C or less, such as about 26°C or less, such as about 24°C or less, such as about 22°C or less, such as about 20°C or less, such as about 18°C or less.

[0032] When a first solvent is provided, it may be provided in portions. For instance, the first solvent may be provided in any number of portions. In particular, the first solvent may be provided directly into the first reagent mixture or reactor volume alone, with the multi-ring aromatic alcohol, and / or with the base.

[0033] In one embodiment, a first portion of the first solvent may be provided with the multi-ring aromatic alcohol. The first portion may include less than the total amount of the first solvent utilized in the first reagent mixture in one embodiment. In another embodiment, the first portion may include the total amount of the first solvent utilized in the first reagent mixture. Accordingly, in providing the first reagent mixture, the method may include a step of providing a multi-ring aromatic alcohol and a first portion of a first solvent, such as in a reactor volume.

[0034] Related, a second portion of the first solvent may be provided with the base. The second portion may include less than the total amount of the first solvent utilized in the first reagent mixture in one embodiment. In another embodiment, the second portion may include the total amount of the first solventutilized in the first reagent mixture. Accordingly, in providing the first reagent mixture, the method may include a step of providing a base and a second portion of a first solvent, such as in a reactor volume.

[0035] Further, a first portion of the first solvent may be provided with the multi-ring aromatic alcohol and a second portion of the first solvent may be provided with the base. The first portion and the second portion may include less than the total amount of the first solvent utilized in the first reagent mixture in one embodiment. In another embodiment, the first portion and the second portion may include the total amount of the first solvent utilized in the first reagent mixture. Accordingly, in providing the first reagent mixture, the method may include a step of providing a multi-ring aromatic alcohol and a first portion of a first solvent, such as in a reactor volume, and providing a base and a second portion of a first solvent, such as in a reactor volume.

[0036] The molar ratio of the base to the multi-ring aromatic alcohol may be within a particular range. For instance, the molar ratio may be 0.1 or more, such as 0.2 or more, such as 0.3 or more, such as 0.4 or more, such as 0.5 or more, such as 0.6 or more, such as 0.7 or more, such as 0.8 or more, such as 0.9 or more, such as 1 or more, such as 1 .1 or more, such as 1.2 or more, such as 1.3 or more, such as 1 .4 or more, such as 1.5 or more, such as 1.6 or more, such as 1 .7 or more, such as 1 .8 or more, such as 1 .9 or more, such as 2 or more. The molar ratio may be 10 or less, such as 8 or less, such as 6 or less, such as 4 or less, such as 3.8 or less, such as 3.6 or less, such as 3.4 or less, such as 3.2 or less, such as 3 or less, such as 2.8 or less, such as 2.6 or less, such as 2.5 or less, such as 2.4 or less, such as 2.3 or less, such as 2.2 or less, such as 2.1 or less, such as 2 or less. In one embodiment, the molar ratio may be from 1.5 to 2.5, such as from 1.7 to 2.5, such as from 1.7 to 2.3, such as from 1 .9 to 2.3, such as from 1.9 to 2.1.

[0037] Related, based on the total moles of the base and the multi-ring aromatic alcohol, the multi-ring aromatic alcohol may be provided in an amount of about 1 mol.% or more, such as about 3 mol.% or more, such as about 5 mol.% or more, such as about 8 mol.% or more, such as about 10 mol.% or more, such as about 13 mol.% or more, such as about 15 mol.% or more, such as about 18 mol.% or more, such as about 20 mol.% or more, such as about 23 mol.% or more,such as about 25 mol.% or more, such as about 28 mol.% or more, such as about 30 mol.% or more, such as about 33 mol.% or more, such as about 35 mol.% or more. The multi-ring aromatic alcohol may be provided in an amount of about 60 mol.% or less, such as about 57 mol.% or less, such as about 55 mol.% or less, such as about 52 mol.% or less, such as about 50 mol.% or less, such as about 48 mol.% or less, such as about 45 mol.% or less, such as about 42 mol.% or less, such as about 40 mol.% or less, such as about 38 mol.% or less, such as about 35 mol.% or less, such as about 33 mol.% or less, such as about 30 mol.% or less based on the total moles of the base and the multi-ring aromatic alcohol. Based on the total moles of the base and the multi-ring aromatic alcohol, the base may be provided in an amount of about 30 mol.% or more, such as about 33 mol.% or more, such as about 35 mol.% or more, such as about 38 mol.% or more, such as about 40 mol.% or more, such as about 43 mol.% or more, such as about 45 mol.% or more, such as about 48 mol.% or more, such as about 50 mol.% or more, such as about 53 mol.% or more, such as about 55 mol.% or more, such as about 58 mol.% or more, such as about 60 mol.% or more, such as about 63 mol.% or more, such as about 65 mol.% or more. The base may be provided in an amount of less than 100 mol.%, such as about 99 mol.% or less, such as about 97 mol.% or less, such as about 95 mol.% or less, such as about 92 mol.% or less, such as about 90 mol.% or less, such as about 87 mol.% or less, such as about 85 mol.% or less, such as about 82 mol.% or less, such as about 80 mol.% or less, such as about 77 mol.% or less, such as about 75 mol.% or less, such as about 72 mol.% or less, such as about 70 mol.% or less, such as about 68 mol.% or less, such as about 65 mol.% or less based on the total moles of the base and the multi-ring aromatic alcohol.

[0038] When utilizing a first solvent, the first solvent may constitute a majority of the first reagent mixture in one embodiment based on the total moles of the multi-ring aromatic alcohol, the base, and the first solvent. For instance, the first solvent may be provided in an amount of about 50 mol.% or more, such as about 55 mol.% or more, such as about 60 mol.% or more, such as about 65 mol.% or more, such as about 70 mol.% or more, such as about 75 mol.% or more, such as about 80 mol.% or more, such as about 85 mol.% or more, such as about 90 mol.% or more, such as about 94 mol.% or more based on the total moles ofthe multi-ring aromatic alcohol, the base, and the first solvent. Related, the multiring aromatic alcohol may be provided in an amount of about 0.1 mol.% or more, such as about 0.2 mol.% or more, such as about 0.3 mol.% or more, such as about 0.4 mol.% or more, such as about 0.5 mol.% or more, such as about 0.6 mol.% or more, such as about 0.7 mol.% or more, such as about 0.8 mol.% or more, such as about 0.9 mol.% or more, such as about 1 mol.% or more, such as about 1.1 mol.% or more, such as about 1.2 mol.% or more, such as about 1 .3 mol.% or more, such as about 1.4 mol.% or more, such as about 1.5 mol.% or more, such as about 1.6 mol.% or more, such as about 1.7 mol.% or more, such as about 1.8 mol.% or more, such as about 1.9 mol.% or more, such as about 2 mol.% or more based on the total moles of the multi-ring aromatic alcohol, the base, and the first solvent. The multi-ring aromatic alcohol may be provided in an amount of about 25 mol.% or less, such as about 20 mol.% or less, such as about 18 mol.% or less, such as about 16 mol.% or less, such as about 14 mol.% or less, such as about 12 mol.% or less, such as about 10 mol.% or less, such as about 8 mol.% or less, such as about 6 mol.% or less, such as about 5 mol.% or less, such as about 4 mol.% or less, such as about 3.3 mol.% or less, such as about 3 mol.% or less, such as about 2.8 mol.% or less, such as about 2.6 mol.% or less, such as about2.5 mol.% or less, such as about 2.4 mol.% or less, such as about 2.3 mol.% or less, such as about 2.2 mol.% or less, such as about 2.1 mol.% or less, such as about 2 mol.% or less, such as about 1.9 mol.% or less, such as about 1.8 mol.% or less based on the total moles of the multi-ring aromatic alcohol, the base, and the first solvent. The base may be provided in an amount of about 0.2 mol.% or more, such as about 0.4 mol.% or more, such as about 0.6 mol.% or more, such as about 0.8 mol.% or more, such as about 1 mol.% or more, such as about 1.2 mol.% or more, such as about 1.4 mol.% or more, such as about 1 .6 mol.% or more, such as about 1 .8 mol.% or more, such as about 2 mol.% or more, such as about 2.2 mol.% or more, such as about 2.4 mol.% or more, such as about 2.6 mol.% or more, such as about 2.8 mol.% or more, such as about 3 mol.% or more, such as about 3.2 mol.% or more, such as about 3.4 mol.% or more, such as about3.6 mol.% or more, such as about 3.8 mol.% or more, such as about 4 mol.% or more based on the total moles of the multi-ring aromatic alcohol, the base, and the first solvent. The base may be provided in an amount of about 50 mol.% or less,such as about 45 mol.% or less, such as about 40 mol.% or less, such as about 35 mol.% or less, such as about 30 mol.% or less, such as about 25 mol.% or less, such as about 20 mol.% or less, such as about 18 mol.% or less, such as about 16 mol.% or less, such as about 14 mol.% or less, such as about 12 mol.% or less, such as about 10 mol.% or less, such as about 8 mol.% or less, such as about 6 mol.% or less, such as about 5.5 mol.% or less, such as about 5 mol.% or less, such as about 4.8 mol.% or less, such as about 4.6 mol.% or less, such as about 4.5 mol.% or less, such as about 4.4 mol.% or less, such as about 4.3 mol.% or less, such as about 4.2 mol.% or less, such as about 4.1 mol.% or less, such as about 4. mol.% or less based on the total moles of the multi-ring aromatic alcohol, the base, and the first solvent.

[0039] As indicated above, the first solvent may be provided in portions in one embodiment. The first portion may be about 5 mol.% or more, such as about 10 mol.% or more, such as about 15 mol.% or more, such as about 20 mol.% or more, such as about 25 mol.% or more, such as about 30 mol.% or more, such as about 35 mol.% or more, such as about 40 mol.% or more, such as about 45 mol.% or more, such as about 50 mol.% or more, such as about 55 mol.% or more, such as about 60 mol.% or more, such as about 65 mol.% or more, such as about 70 mol.% or more, such as about 75 mol.% or more, such as about 80 mol.% or more, such as about 85 mol.% or more, such as about 90 mol.% or more, such as about 95 mol.% or more based on the total moles of the first solvent. The first portion may be 100 mol.% or less, such as about 95 mol.% or less, such as about 90 mol.% or less, such as about 85 mol.% or less, such as about 80 mol.% or less, such as about 75 mol.% or less, such as about 70 mol.% or less, such as about 65 mol.% or less, such as about 60 mol.% or less, such as about 55 mol.% or less, such as about 50 mol.% or less, such as about 45 mol.% or less, such as about 40 mol.% or less, such as about 35 mol.% or less, such as about 30 mol.% or less, such as about 25 mol.% or less, such as about 20 mol.% or less, such as about 15 mol.% or less, such as about 10 mol.% or less based on the total moles of the first solvent.

[0040] In this regard, when providing a first portion of the first solvent with the multi-ring aromatic alcohol, the molar ratio of the first portion of the first solvent to the multi-ring aromatic alcohol may be about 0.1 or more, such as about 0.5 ormore, such as about 1 or more, such as about 2 or more, such as about 3 or more, such as about 4 or more, such as about 5 or more, such as about 8 or more, such as about 10 or more, such as about 13 or more, such as about 15 or more, such as about 20 or more, such as about 23 or more, such as about 25 or more, such as about 28 or more, such as about 30 or more, such as about 33 or more, such as about 35 or more, such as about 38 or more, such as about 40 or more. The molar ratio of the first portion of the first solvent to the multi-ring aromatic alcohol may be about may be about 100 or less, such as about 95 or less, such as about 90 or less, such as about 85 or less, such as about 80 or less, such as about 75 or less, such as about 70 or less, such as about 65 or less, such as about 60 or less, such as about 57 or less, such as about 55 or less, such as about 53 or less, such as about 50 or less, such as about 48 or less, such as about 45 or less, such as about 43 or less.

[0041] In one embodiment, the second portion may be about 5 mol.% or more, such as about 10 mol.% or more, such as about 15 mol.% or more, such as about 20 mol.% or more, such as about 25 mol.% or more, such as about 30 mol.% or more, such as about 35 mol.% or more, such as about 40 mol.% or more, such as about 45 mol.% or more, such as about 50 mol.% or more, such as about 55 mol.% or more, such as about 60 mol.% or more, such as about 65 mol.% or more, such as about 70 mol.% or more, such as about 75 mol.% or more, such as about 80 mol.% or more, such as about 85 mol.% or more, such as about 90 mol.% or more, such as about 95 mol.% or more based on the total moles of the first solvent. The second portion may be 100 mol.% or less, such as about 95 mol.% or less, such as about 90 mol.% or less, such as about 85 mol.% or less, such as about 80 mol.% or less, such as about 75 mol.% or less, such as about 70 mol.% or less, such as about 65 mol.% or less, such as about 60 mol.% or less, such as about 55 mol.% or less, such as about 50 mol.% or less, such as about 45 mol.% or less, such as about 40 mol.% or less, such as about 35 mol.% or less, such as about 30 mol.% or less, such as about 25 mol.% or less, such as about 20 mol.% or less, such as about 15 mol.% or less, such as about 10 mol.% or less based on the total moles of the first solvent.

[0042] In this regard, when providing a second portion of the first solvent with the base, the molar ratio of the second portion of the first solvent to the basemay be about 0.1 or more, such as about 0.5 or more, such as about 1 or more, such as about 1 .5 or more, such as about 2 or more, such as about 2.5 or more, such as about 3 or more, such as about 3.5 or more, such as about 4 or more, such as about 4.5 or more, such as about 5 or more. The molar ratio of the second portion of the first solvent to the base may be about may be about 100 or less, such as about 95 or less, such as about 90 or less, such as about 85 or less, such as about 80 or less, such as about 75 or less, such as about 70 or less, such as about 65 or less, such as about 60 or less, such as about 55 or less, such as about 50 or less, such as about 45 or less, such as about 40 or less, such as about 35 or less, such as about 30 or less, such as about 25 or less, such as about 20 or less, such as about 15 or less, such as about 10 or less, such as about 8 or less, such as about 7.5 or less, such as about 7 or less, such as about 6.5 or less, such as about 6 or less, such as about 5.5 or less.

[0043] When providing the multi-ring aromatic alcohol and the base, it may be desired to have a relatively low water content. Related, when providing the multi-ring aromatic alcohol, the base, and the first solvent, it may be desired to have a relatively low water content. Such a low water content may facilitate the reaction. In this regard, one or more of the components may be dried to remove any water prior to providing in the reactor volume and / or forming the first reagent mixture. The water content of each individual component or collectively in combination may be 15 wt.% or less, such as 12 wt.% or less, such as 10 wt.% or less, such as 8 wt.% or less, such as 6 wt.% or less, such as 4 wt.% or less, such as 3 wt.% or less, such as 2 wt.% or less, such as 1 wt.% or less, such as 0.8 wt.% or less, such as 0.5 wt.% or less, such as 0.4 wt.% or less, such as 0.3 wt.% or less, such as 0.2 wt.% or less, such as 0.1 wt.% or less. Such weight percentage may be based on the weight of an individual component or the combination of any two components (e.g., multi-ring aromatic alcohol and base) or three components.

[0044] Regarding the reactor volume, it should be understood that it may constitute the volume of any reactor that may be utilized for the reaction as described herein. For instance, such reactor may be any type of apparatus that may be used in an ordinary Kolbe-Schmitt type reaction. In this regard, it may be any vessel, container, or other structure that can be utilized for the reaction asdescribed herein. As an example, this may include an autoclave equipped with a stirrer and capable of handling high-pressure reactions.

[0045] After the providing step, the method may further include a reacting step. For instance, the reacting step may include reacting the multi-ring aromatic alcohol and the base to form a first intermediate mixture comprising a salt of the multi-ring aromatic alcohol and water. For instance, the reaction may create water for each salicylate group that may be formed. In addition, the first intermediate mixture may also include the optional first solvent. If a first solvent is utilized, the first intermediate mixture may include a salt of the multi-ring aromatic alcohol, water, and the first solvent. If the base is utilized in excess, the first intermediate mixture may include the base in one embodiment. In this regard, the first intermediate mixture may include a salt of the multi-ring aromatic alcohol, water, and the base and if the first solvent is utilized, also the first solvent.

[0046] For the reacting step, the first reagent mixture and / or the reactor volume may be heated. In this regard, the method may include a step of heating the first reagent mixture. Related, the method may include a step of heating the reactor volume. In this regard, the resulting temperature may be about 15°C or more, such as about 18°C or more, such as about 20°C or more, such as about 22°C or more, such as about 24°C or more. The temperature may be about 300°C or less, such as 260°C or less, such as about 220°C or less, such as about 180°C or less, such as about 140°C or less, such as about 120°C or less, such as about 100°C or less, such as about 90°C or less, such as about 80°C or less, such as about 75°C or less, such as about 70°C or less, such as about 65°C or less, such as about 60°C or less, such as about 56°C or less, such as about 52°C or less, such as about 48°C or less, such as about 44°C or less, such as about 40°C or less, such as about 36°C or less, such as about 32°C or less, such as about 28°C or less, such as about 26°C or less.

[0047] Next, in certain embodiments, the method may include a step of adding a second solvent to the reactor volume, such as to form a second intermediate mixture. In this regard, the second intermediate mixture may include the salt of the multi-ring aromatic alcohol and the second solvent. Further, the second intermediate mixture may also include water and / or the optional first solvent. In this regard, the second intermediate mixture may include the salt of themulti-ring aromatic alcohol, the second solvent, and water. In addition, if the first solvent was utilized and removal has not occurred, the second intermediate mixture may also include water and the first solvent. In this regard, the second intermediate mixture may include the salt of the multi-ring aromatic alcohol, the second solvent, water, and the first solvent.

[0048] In certain other embodiments, the method may include a step of adding a second solvent to the reactor volume and removing at least partially the water from the reactor volume. In addition, the optional first solvent may also at least partially be removed. If a first solvent is utilized, both water and the first solvent may at least partially be removed from the reactor volume. Without intending to be limited, such addition and removal may be referred to as a solvent exchange.

[0049] In one embodiment, the addition of the second solvent may occur at a desired time during the reaction. For instance, the second solvent may be added prior to beginning the removal step. In this regard, the second intermediate mixture may include the salt of the multi-ring aromatic alcohol and the second solvent. Further, as the removal may not have yet occurred, the second intermediate mixture may also include water and / or the optional first solvent. In this regard, the second intermediate mixture may include the salt of the multi-ring aromatic alcohol, the second solvent, and water. In addition, if the first solvent was utilized and removal may not have yet occurred, the second intermediate mixture may also include water and the first solvent. In this regard, the second intermediate mixture may include the salt of the multi-ring aromatic alcohol, the second solvent, water, and the first solvent.

[0050] In another embodiment, the second solvent may be provided after the completion of the aforementioned removal step. In a further embodiment, the second solvent may be provided at the same time as the removal step. In a further embodiment, the addition of the second solvent may occur after the removal step has been initiated. In this regard, the addition of the second solvent may occur prior to completion of the removal step. In one embodiment, such addition of the second solvent and removal of the water (and optional first solvent) may occur using solvent exchange techniques as generally known in the art.

[0051] Regardless, the second intermediate mixture may include the salt of the multi-ring aromatic alcohol and the second solvent. Further, as the removal step may not have yet been completed or even if the removal step has been completed, the second intermediate mixture may also include any residual water and / or residual optional first solvent. Such residual water and / or residual optional first solvent may be present because it was not removed during the removal step. In this regard, the second intermediate mixture may include the salt of the multiring aromatic alcohol, the second solvent, and residual water. In addition, if the first solvent was utilized and removal may not have yet been completed or even if the removal step has been completed, the second intermediate mixture may also include residual water and / or residual first solvent. In this regard, the second intermediate mixture may include the salt of the multi-ring aromatic alcohol, the second solvent, and residual water and / or residual first solvent. In one embodiment, the second intermediate mixture may include the salt of the multi-ring aromatic alcohol, the second solvent, residual water, and residual first solvent.

[0052] Regarding the removal, it may be conducted via distillation, evaporation, or other removal techniques as generally known in the art. In one embodiment, the removal may be conducted via distillation. In one embodiment, the reactor volume may be placed under an inert atmosphere. For example, the inert gas may include nitrogen or argon. In one embodiment, the inert gas may include nitrogen.

[0053] Further, the temperature at which distillation may occur may be dependent upon the boiling temperature (at atmospheric pressure) of the second solvent if present as well as the boiling temperature (at atmospheric pressure) of the first solvent if present and of course, the boiling temperature (at atmospheric pressure) of water. In this regard, the temperature of a respective intermediate mixture and / or the reactor volume may be increased to at least the boiling temperature of the first solvent if present and subsequently to at least 100°C. For instance, for the removal, the final temperature may be at least 100°C, such as at least 105°C, such as at least 110°C, such as at least 115°C, such as at least 120°C, such as at least 130°C, such as at least 140°C, such as at least 150°C. The temperature may be less than the boiling temperature (at atmospheric pressure) of the second solvent if present. For instance, the temperature may be250°C or less, such as 230°C or less, such as 210°C or less, such as 190°C or less, such as 170°C or less, such as 150°C or less, such as 140°C or less, such as 130°C or less, such as 120°C or less, such as 110°C or less.

[0054] The removal may result in a majority of the total water present being removed from the reactor volume. For instance, the removal may result in at least 50 wt.% or more, such as at least 60 wt.% or more, such as at least 70 wt.% or more, such as at least 80 wt.% or more, such as at least 85 wt.% or more, such as at least 90 wt.% or more, such as at least 93 wt.% or more, such as at least 95 wt.% or more, such as at least 97 wt.% or more, such as at least 98 wt.% or more, such as at least 99 wt.% or more, such as at least 99.5 wt.% or more of the total water being removed from the reactor volume. Related, when present, the removal may result in a majority of the total first solvent present being removed from the reactor volume. For instance, such removal may result in at least 50 wt.% or more, such as at least 60 wt.% or more, such as at least 70 wt.% or more, such as at least 80 wt.% or more, such as at least 85 wt.% or more, such as at least 90 wt.% or more, such as at least 93 wt.% or more, such as at least 95 wt.% or more, such as at least 97 wt.% or more, such as at least 98 wt.% or more, such as at least 99 wt.% or more, such as at least 99.5 wt.% or more of the total first solvent being removed from the reactor volume. Further, when the first solvent is present, such removal may result in at least 50 wt.% or more, such as at least 60 wt.% or more, such as at least 70 wt.% or more, such as at least 80 wt.% or more, such as at least 85 wt.% or more, such as at least 90 wt.% or more, such as at least 93 wt.% or more, such as at least 95 wt.% or more, such as at least 97 wt.% or more, such as at least 98 wt.% or more, such as at least 99 wt.% or more, such as at least 99.5 wt.% or more of the total combined weight of the water and the first solvent being removed from the reactor volume.

[0055] In this regard, upon removing any water, the second intermediate mixture may include 10 wt.% or less, such as 8 wt.% or less, such as 6 wt.% or less, such as 5 wt.% or less, such as 4.5 wt.% or less, such as 4 wt.% or less, such as 3.5 wt.% or less, such as 3 wt.% or less, such as 2.5 wt.% or less, such as 2 wt.% or less, such as 1 .5 wt.% or less, such as 1 wt.% or less, such as 0.8 wt.% or less, such as 0.6 wt.% or less, such as 0.4 wt.% or less, such as 0.2 wt.% or less, such as 0.1 wt.% or less, such as 0.05 wt.% or less, such as 0.01 wt.% orless of water. Similarly, upon removing any first solvent, the second intermediate mixture may include 10 wt.% or less, such as 8 wt.% or less, such as 6 wt.% or less, such as 5 wt.% or less, such as 4.5 wt.% or less, such as 4 wt.% or less, such as 3.5 wt.% or less, such as 3 wt.% or less, such as 2.5 wt.% or less, such as 2 wt.% or less, such as 1 .5 wt.% or less, such as 1 wt.% or less, such as 0.8 wt.% or less, such as 0.6 wt.% or less, such as 0.4 wt.% or less, such as 0.2 wt.% or less, such as 0.1 wt.% or less, such as 0.05 wt.% or less, such as 0.01 wt.% or less of the first solvent.

[0056] As indicated herein, the reaction of the multi-ring aromatic alcohol and the base may yield a salt of the multi-ring aromatic alcohol. The salt may be an alkali salt, such as when utilizing an alkali for the base. Furthermore, the salt may be a disalt, such as a dialkali salt, when utilizing an alkali for the base. In one embodiment, upon removing the water and / or the first solvent, a salt of the multiring aromatic alcohol may be formed. In particular, a salt of the multi-ring aromatic alcohol may be precipitated.

[0057] Accordingly, in one embodiment, rather than beginning with a multiring aromatic alcohol and a base, the reaction may begin with a second reagent mixture comprising a salt of the multi-ring aromatic alcohol. In addition, the second reagent mixture may comprise a second solvent. Accordingly, the second reagent mixture may comprise a salt of the multi-ring aromatic alcohol and a second solvent. Depending on the purity of the salt of the multi-ring aromatic alcohol, the second reagent mixture may comprise residual multi-ring aromatic alcohol (e.g., that utilized to form the salt), water, etc. In one embodiment, the second reagent mixture may also include a base as defined herein.

[0058] Regardless, the method may include a step of providing a second reagent mixture including a salt of a multi-ring aromatic alcohol and a second solvent. By providing the second reagent mixture, it may be provided in a reactor volume. In this regard, the second reagent mixture may be provided by forming prior to providing into the reactor volume in one embodiment. In another embodiment, the second reagent mixture may be provided by forming within the reactor volume.

[0059] In providing the second reagent mixture, if providing the reagents separately to the reactor volume, the order is not necessarily limited. For instance,in one embodiment, the second solvent may be provided and then the salt of a multi-ring aromatic alcohol may be provided. In another embodiment, the salt of a multi-ring aromatic alcohol may first be provided and then the second solvent may be provided. Regardless, the providing step, whether individually or collectively, may be at a temperature of about 10°C or more, such as about 12°C or more, such as about 14°C or more, such as about 16°C or more, such as about 18°C or more, such as about 20°C or more, such as about 22°C or more, such as about 24°C or more. The providing step may be at a temperature of about 60°C or less, such as about 56°C or less, such as about 52°C or less, such as about 48°C or less, such as about 44°C or less, such as about 40°C or less, such as about 36°C or less, such as about 32°C or less, such as about 28°C or less, such as about 26°C or less, such as about 24°C or less, such as about 22°C or less, such as about 20°C or less, such as about 18°C or less.

[0060] The second solvent may constitute a majority of the second reagent mixture in one embodiment based on the total moles of the salt of the multi-ring aromatic alcohol and the second solvent. For instance, in one embodiment, the second solvent may be provided in an amount of about 50 mol.% or more, such as about 55 mol.% or more, such as about 60 mol.% or more, such as about 65 mol.% or more, such as about 70 mol.% or more, such as about 75 mol.% or more, such as about 80 mol.% or more, such as about 85 mol.% or more, such as about 90 mol.% or more, such as about 94 mol.% or more based on the total moles of the salt of the multi-ring aromatic alcohol and the second solvent. Related, the salt of the multi-ring aromatic alcohol may be provided in an amount of about 0.1 mol.% or more, such as about 0.2 mol.% or more, such as about 0.3 mol.% or more, such as about 0.4 mol.% or more, such as about 0.5 mol.% or more, such as about 0.8 mol.% or more, such as about 1 mol.% or more, such as about 2 mol.% or more, such as about 3 mol.% or more, such as about 5 mol.% or more, such as about 7 mol.% or more, such as about 10 mol.% or more, such as about 12 mol.% or more, such as about 14 mol.% or more, such as about 16 mol.% or more, such as about 18 mol.% or more, such as about 20 mol.% or more based on the total moles of the salt of the multi-ring aromatic alcohol and the second solvent. The salt of the multi-ring aromatic alcohol may be provided in an amount of about 45 mol% or less, such as about 40 mol.% or less, such as about 35 mol.% or less,such as about 30 mol.% or less, such as about 28 mol.% or less, such as about 26 mol.% or less, such as about 24 mol.% or less, such as about 22 mol.% or less, such as about 20 mol.% or less, such as about 18 mol.% or less, such as about 16 mol.% or less, such as about 14 mol.% or less, such as about 12 mol.% or less, such as about 10 mol.% or less based on the total moles of the salt of the multiring aromatic alcohol and the second solvent.

[0061] When providing the salt of the multi-ring aromatic alcohol and the second solvent, it may be desired to have a relatively low water content. Such a low water content may facilitate the reaction. In this regard, one or more of the components may be dried to remove any water prior to providing in the reactor volume and / or forming the second reagent mixture. The water content of each individual component or collectively in combination may be 15 wt.% or less, such as 12 wt.% or less, such as 10 wt.% or less, such as 8 wt.% or less, such as 6 wt.% or less, such as 4 wt.% or less, such as 3 wt.% or less, such as 2 wt.% or less, such as 1 wt.% or less, such as 0.8 wt.% or less, such as 0.5 wt.% or less, such as 0.4 wt.% or less, such as 0.3 wt.% or less, such as 0.2 wt.% or less, such as 0.1 wt.% or less. Such weight percentage may be based on the weight of an individual component or the combination of two components.

[0062] Further, the reactor volume may be as defined herein with respect to the method beginning with the multi-ring aromatic alcohol and the base.

[0063] Regardless of whether beginning with the multi-ring aromatic alcohol or the salt of the multi-ring aromatic alcohol, the method may include a step of adding CO2, for instance to the reactor volume. In one embodiment, the CO2 may at least partially dissolve in the second solvent to assist in the carboxylation reaction. In this regard, the method may include a step of reacting the salt of the multi-ring aromatic alcohol and the CO2 to form a reaction product mixture comprising a multi-ring disalicylate compound and / or a salt thereof.

[0064] In particular, the method may include a step of reacting the salt of the multi-ring aromatic alcohol and the CO2 to form a reaction product mixture comprising a salt of a multi-ring disalicylate compound in one embodiment. When utilizing an alkali for a base in the first reagent mixture or if present in the second reagent mixture, the salt may be an alkali salt, in particular a dialkali salt, of the multi-ring disalicylate compound.

[0065] The reactor volume can be heated and pressurized with CO2 as desired for the reaction. Accordingly, such CO2 exposure may be under relatively low or high temperature and / or relatively low- or high-pressure conditions as desired and mentioned herein.

[0066] Furthermore, the reactor volume can be heated and pressurized in any convenient order. For example, the reactor volume may initially be pressurized to a first pressure value by addition of gas phase CO2 at a certain temperature (e.g., from 15°C to 30°C, such as from 15°C to 25°C, such as near 17°C or near 25°C). After adding the desired amount of CO2, the reactor volume can then be heated. This may result in further increases in pressure due to the CO2 either being in the gas phase or being present as a supercritical fluid. The pressurization and heating can be performed in any convenient manner to achieve a target set of conditions for performing the reaction to form the multi-ring disalicylate compound.

[0067] In one embodiment, the CO2 may be provided and present in a non- supercritical (or sub-supercritical) state. For instance, the temperature and / or pressure may be such that the CO2 provided is not in a supercritical state.

[0068] The amount of CO2 utilized may be any convenient amount so that a molar excess of CO2 is present in the reactor volume relative to the amount of multi-ring aromatic alcohol and / or salt of the multi-ring aromatic alcohol, such as having a molar amount of CO2 that is at least 2 times, such as at least 3 times, such as at least 4 times, such as at least 5 times the molar amount of the multi-ring aromatic alcohol or salt thereof. In this regard, after an initial introduction of CO2 to the reactor volume, subsequent additions of CO2 as desired may also be provided to the reactor volume. For instance, such subsequent introductions may also be at the temperature and pressure conditions as mentioned herein.

[0069] In one embodiment, the reaction may occur at a temperature at or above the boiling temperature (at atmospheric pressure) of the second solvent. In another embodiment, the reaction may occur at a temperature below the boiling temperature (at atmospheric pressure) of the second solvent. The temperature may be 320°C or less, such as 300°C or less, such as 290°C or less, such as 270°C or less, such as 250°C or less, such as 240°C or less, such as 230°C or less, such as 220°C or less, such as 210°C or less, such as 200°C or less, such as190°C or less, such as 170°C or less, such as 150°C or less, such as 140°C or less, such as 130°C or less, such as 120°C or less. The temperature may be at least 100°C, such as at least 110°C, such as at least 120°C, such as at least 130°C, such as at least 140°C, such as at least 150°C, such as at least 160°C, such as at least 170°C, such as at least 180°C, such as at least 190°C, such as at least 200°C, such as at least 210°C, such as at least 220°C, such as at least 230°C. The temperature may be maintained as necessary within a target range for a desired reaction time.

[0070] Regarding the pressure, in various embodiments, the total pressure in the reactor volume may be maintained at a pressure of 0.1 MPa or more, such as 0.2 MPa or more, such as 0.3 MPa or more, such as 0.4 MPa or more, such as 0.5 MPa or more, such as 0.6 MPa or more, such as 0.7 MPa or more, such as 0.8 MPa or more, such as 0.9 MPa or more, such as 1 MPa or more, such as 1 .3 MPa or more, such as 1 .6 MPa or more, such as 1 .9 MPa or more, such as 2.2 MPa or more, such as 2.5 MPa or more, such as 2.8 MPa or more, such as 3.1 MPa or more, such as 3.4 MPa or more, such as 3.7 MPa or more, such as 4 MPa or more, such as 4.4 MPa or more, such as 4.8 MPa or more, such as 5.2 MPa or more, such as 5.6 MPa or more, such as 6 MPa or more, such as 6.5 MPa or more, such as 7 MPa or more. The total pressure may be 20 MPa or less, such as 16 MPa or less, such as 12 MPa or less, such as 10 MPa or less, such as 9 MPa or less, such as 8 MPa or less, such as 7MPa or less, such as 6 MPa or less, such as 5 MPa or less, such as 4 MPa or less, such as 3 MPa or less, such as 2 MPa or less, such as 1.5 MPa or less, such as 1.3 MPa or less, such as 1.1 MPa or less, such as 1 MPa or less, such as 0.9 MPa or less, such as 0.8 MPa or less, such as 0.7 MPa or less, such as 0.6 MPa or less, such as 0.5 MPa or less.

[0071] Regarding the pressure, in various embodiments, the CO2 pressure in the reactor volume may be maintained at a pressure of 0.1 MPa or more, such as 0.2 MPa or more, such as 0.3 MPa or more, such as 0.4 MPa or more, such as 0.5 MPa or more, such as 0.6 MPa or more, such as 0.7 MPa or more, such as 0.8 MPa or more, such as 0.9 MPa or more, such as 1 MPa or more, such as 1 .3 MPa or more, such as 1 .6 MPa or more, such as 1 .9 MPa or more, such as 2.2 MPa or more, such as 2.5 MPa or more, such as 2.8 MPa or more, such as 3.1 MPa or more, such as 3.4 MPa or more, such as 3.7 MPa or more, such as 4 MPa ormore, such as 4.4 MPa or more, such as 4.8 MPa or more, such as 5.2 MPa or more, such as 5.6 MPa or more, such as 6 MPa or more, such as 6.5 MPa or more, such as 7 MPa or more. The CO2 pressure may be 20 MPa or less, such as 16 MPa or less, such as 12 MPa or less, such as 10 MPa or less, such as 9 MPa or less, such as 8 MPa or less, such as 7MPa or less, such as 6 MPa or less, such as 5 MPa or less, such as 4 MPa or less, such as 3 MPa or less, such as 2 MPa or less, such as 1.5 MPa or less, such as 1.3 MPa or less, such as 1.1 MPa or less, such as 1 MPa or less, such as 0.9 MPa or less, such as 0.8 MPa or less, such as 0.7 MPa or less, such as 0.6 MPa or less, such as 0.5 MPa or less.

[0072] In some embodiments, the pressure can be maintained below the supercritical point for pure CO2. In other embodiments, the pressure may be maintained at or above the supercritical point for pure CO2. For instance, the CO2 pressure may be at or above the pressure necessary to obtain supercritical CO2 at the particular reaction temperature.

[0073] Further, in one embodiment, the carboxylation may be conducted at a relatively low pressure. For instance, in some embodiments, the pressure can be maintained below the supercritical point for pure CO2. Accordingly, the CO2 may be in a sub-supercritical state, such as at a sub-supercritical pressure based on the temperature. However, in another embodiment, the pressure may be maintained at or above the supercritical point for pure CO2 based on the reaction temperature. Accordingly, the CO2 may be in a supercritical state.

[0074] Furthermore, the total pressure within the reactor volume may correspond to the CO2 pressure in some embodiments. However, it should be understood that the total pressure may be higher than the CO2 pressure due to the presence of other fluids. For example, any water, such as any residual water as defined herein, may be present within the reactor volume and may contribute to the total pressure being slightly higher than the CO2 pressure.

[0075] Further, the reaction may be allowed to proceed within a target temperature range and / or target pressure range for a reaction time of 0.5 hours or more, such as 1 hour or more, such as 2 hours or more, such as 3 hours or more, such as 4 hours or more, such as 5 hours or more, such as 6 hours or more, such as 7 hours or more, such as 8 hours or more, such as 9 hours or more, such as 10 hours or more, such as 12 hours or more, such as 14 hours or more, such as 16hours or more, such as 18 hours or more, such as 20 hours or more, such as 22 hours or more, such as 24 hours or more, such as 26 hours or more, such as 28 hours or more. The reaction time may be 50 hours or less, such as 46 hours or less, such as 44 hours or less, such as 42 hours or less, such as 38 hours or less, such as 34 hours or less, such as 30 hours or less, such as 26 hours or less, such as 22 hours or less, such as 18 hours or less, such as 14 hours or less, such as 10 hours or less, such as 8 hours or less, such as 6 hours or less, such as 4 hours or less, such as 3.5 hours or less, such as 3 hours or less, such as 2.5 hours or less, such as 2 hours or less, such as 1.5 hours or less, such as 1 hour or less. However, it should be understood that shorter or longer reaction times may be utilized as necessary.

[0076] In one embodiment, the reaction with the CO2 may be conducted in the presence of an organic acid and / or an organic acid salt. The organic acid and / or an organic acid salt may include acetic acid, formic acid, propionic acid, oxalic acid, malonic acid, succinic acid, glutamic acid, adipic acid, maleic acid, fumaric acid, phthalic acid, tartaric acid, citric acid, or a salt thereof as well as combinations thereof. The salt may include an alkali salt, such as a sodium salt, a potassium salt, a lithium salt, a rubidium salt, and / or a cesium salt. In this regard, the organic acid or salt thereof may include sodium formate, sodium acetate, potassium formate, potassium acetate, lithium acetate, rubidium acetate, or cesium acetate. Further, when adding an organic acid and / or an organic acid salt, it may be provided in an amount of 0.1 to 10 mol, such as 0.3 to 5 mol, such as 0.5 to 4.5 mol, such as 1 to 3 mol per mole of the multi-ring aromatic alcohol or salt thereof.

[0077] In one embodiment, the reaction with the CO2 may not be conducted in the presence of an organic acid and / or an organic acid salt. For instance, such an organic acid and / or an organic acid salt may not be provided to the reactor volume or respective mixture (e.g., second reagent mixture, second intermediate mixture) in one embodiment.

[0078] While the aforementioned refers to the use of a second solvent, it should be understood that in some embodiments, a second solvent may not be utilized. Without intending to be limited, such embodiments may be when the CO2 is provided in a supercritical or near-supercritical state. Regardless, in someembodiments, the reagents in the reaction environment may consist essentially of or consist of the multi-ring aromatic alcohol or a salt thereof, the base, and CO2. For instance, in one embodiment wherein the starting materials include the first reagent mixture including the multi-ring aromatic alcohol and the base, the reagents in the reaction environment may consist essentially of or consist of the multi-ring aromatic alcohol, the base, and CO2. In another embodiment wherein the starting materials include the second reagent mixture including the salt of the multi-ring aromatic alcohol, the reagents in the reaction environment may consist essentially of or consist of the salt of the multi-ring aromatic alcohol and CO2. In such latter embodiments, the reagents may also include a second solvent if utilized.

[0079] Nevertheless, in such embodiments, other components can be in the reaction environment, such as inert gases (e.g., N2). Additionally, in such embodiments, water may be present due to hydration associated with the reagents, although in some embodiments it may be preferable to dry the reagents to remove water prior to synthesis and reaction with the CO2.

[0080] The reaction product mixture comprises the multi-ring disalicylate compound and / or a salt thereof. In one embodiment, the reaction product mixture comprises a salt of the multi-ring disalicylate compound. However, the reaction product mixture may be a crude mixture in one embodiment. For instance, it may include impurities such as reagents, solvents, etc., that may not have been removed or consumed during the synthesis.

[0081] Depending on the reaction mechanism and solvent utilized, the multiring disalicylate compound and / or salt thereof may be present in a dissolved form or a precipitated form. Regardless of the form, the reaction product mixture can be separated from any liquid, such as the second solvent, using standard separation techniques known in the art. For instance, if in a dissolved form, the reaction product mixture may be separated using evaporation or distillation. If in a precipitated form, the means may be those generally known in the art of liquidsolid separations, such as filtration, evaporation, or distillation. In this regard, the method may include a step of separating the second solvent from the reaction product mixture.

[0082] The reaction product mixture may then be further purified (or refined). Prior to purification, the reaction product mixture may have an impurity content of 40 wt.% or less, such as 35 wt.% or less, such as 30 wt.% or less, such as 25 wt.% or less, such as 20 wt.% or less, such as 18 wt.% or less, such as 15 wt.% or less, such as 13 wt.% or less, such as 10 wt.% or less, such as 8 wt.% or less, such as 6 wt.% or less, such as 4 wt.% or less, such as 3 wt.% or less, such as 2 wt.% or less, such as 1 wt.% or less based on the weight of the reaction product mixture. These impurities may include other components, such as raw materials (e.g., multi-ring aromatic alcohol, first solvent, second solvent, and / or by-products, etc. other than the multi-ring disalicylate compound or salt thereof).

[0083] In this regard, the method may include a step of purifying the reaction product mixture to form a purified product mixture. For instance, such purification may include washing, selective dissolution, recrystallization, and / or reprecipitation or any other purification generally known in the art. In one embodiment, such purification may be conducted via washing (e.g., suspension washing). For instance, the reaction product mixture may be washed with water, such as deionized water, and / or an organic compound such as methanol, ethanol, n-propyl alcohol, isopropyl alcohol, 2-ethylhexanol, ethylene glycol, glycerin, acetic acid, N- methyl-2-pyrrolidone, dimethylformamide, acetonitrile, acetone, xylene, toluene, methyl ethyl ketone, methyl isobutyl ketone, hexane, heptane, cyclohexanone, tetrahydrofuran, 4-methyltetrahydropyran, chloroform, dioxane, methyl-tert butyl ether, ethyl acetate, propyl acetate, and / or butyl acetate. In one embodiment, the reaction product mixture may be washed with water, such as deionized water. In another embodiment, the reaction product mixture may be washed with an aqueous solution, such as a solution including water and any of the aforementioned organic compounds.

[0084] The amount of liquid (e.g., water and / or organic compound) utilized in the washing may vary depending on the particular type utilized. Accordingly, the amount is not necessarily limited by the present disclosure. Nevertheless, it may vary from 1 to 50 times the mass of the reaction product mixture. Further, the temperature at which the washing is conducted is not particularly limited. The temperature may be from 15°C to 200°C, such as from 20°C to 150°C, such as from 25°C to 100°C.

[0085] In addition to the above, it should be understood that other or subsequent re-crystallization steps may also be performed to increase the product purity. For instance, recrystallization may be conducted using a recrystallization solvent and then crystalizi ng the multi-ring disalicylate compound or salt thereof, in particular the salt of the multi-ring disalicylate compound. The amount of the recrystallization solvent and the temperature is not necessarily limited by the present disclosure and can be selected using means generally known in the art.

[0086] Also, reprecipitation may be performed by adding a poor solvent to a solution in which the multi-ring disalicylate compound or salt thereof, in particular the salt of the multi-ring disalicylate compound, is dissolved in a good solvent. The good solvent and poor solvent used in the reprecipitation step can be appropriately selected from among the solvents used in the purification step. In general, a poor solvent may be one in which the solubility of a specific compound or salt is <0.1 g / L in the solvent. Meanwhile, a good solvent may be one in which the solubility of a specific compound or salt is >0.1 g / L.

[0087] In one embodiment, purification may be conducted via selective dissolution. During selective dissolution, a solvent may be introduced to selectively dissolve a particular compound or salt (e.g., a particular impurity) wherein such solvent may be generally insoluble with respect to other compounds (e.g., desired products). In this regard, such selective dissolution may allow for selective removal of any particular impurities. Without intending to be limited, such selective dissolution may allow for an effective reaction for yielding a desired product. For instance, rather than dissolving a desired product and then recovering such desired product, the desired product may remain in its original form while any impurities may be removed.

[0088] In this regard for selective dissolution, the reaction product mixture comprising the multi-ring disalicylate compound and / or salt thereof, in particular the salt of the multi-ring disalicylate compound in one embodiment, may be introduced to a third solvent. The reaction product mixture may also include one or more impurities. For instance, one of such impurities may include the multi-ring aromatic alcohol or salt thereof. In one embodiment, the impurity may be the multi-ring aromatic alcohol. In another embodiment, the impurity may be the salt of the multi-ring aromatic alcohol. In a further embodiment, the impurity be the multi-ring aromatic alcohol and a salt thereof. In this regard, such third solvent may be a good solvent for any of the one or more impurities, such as the multi-ring aromatic alcohol and / or salt thereof, in the reaction product mixture.

[0089] Via selective dissolution, the reaction product mixture, in particular the crude mixture, may be contacted with the third solvent (or the good solvent for the one or more impurities such as the multi-ring aromatic alcohol and / or salt thereof). In this regard, the third solvent may be a poor solvent for the salt of the multi-ring disalicylate compound in one embodiment. The manner in which the contact occurs is not limited by the present disclosure. In one embodiment, the reaction product mixture, in particular the crude mixture, may be mixed with the good solvent. Such mixing may be by adding the reaction product mixture, in particular the crude mixture, to the third solvent and forming a suspension or dispersion. In the end, the third solvent may dissolve the respective impurity, such as the multi-ring aromatic alcohol and / or salt thereof. Upon dissolution, standard liquid-solid separation, such as filtration, may be utilized to separate the reaction product mixture from the third solvent, in particular the third solvent including the dissolved one or more impurities, such as the multi-ring aromatic alcohol and / or salt thereof.

[0090] As indicated above, the impurity may include at least the multi-ring aromatic alcohol and / or salt thereof in one embodiment. Such multi-ring aromatic alcohol may include biphenol. In this regard, the impurity may be biphenol and / or a salt thereof. The third solvent may include any solvent which may dissolve one or more of the impurities. For instance, it may be any solvent that may dissolve biphenol in one embodiment. In one embodiment, the solvent may be a ketone. For instance, the ketone may be acetone, methyl ethyl ketone, or a mixture thereof. In one particular embodiment, the solvent may be methyl ethyl ketone. In another particular embodiment, the solvent may be acetone. In one particular embodiment, selective dissolution may be utilized to remove the biphenol and / or salt thereof from the reaction product mixture, in particular the crude mixture, including the salt of the multi-ring disalicylate compound.

[0091] During the selective dissolution, in one embodiment, the method may also include a step of adding an acid to the reaction product mixture, such as the crude mixture. Such acid may be utilized to selectively convert any salt of themulti-ring aromatic alcohol to the multi-ring aromatic alcohol. The acid may be a mineral acid in one embodiment. In another embodiment, the acid may be an oxoacid. In a further embodiment, the acid may be a strong acid. The acid may be sulfuric acid, hydrochloric acid, hydrofluoric acid, nitric acid, phosphoric acid, perchloric acid, etc. In one embodiment, the acid may be hydrochloric acid. In another embodiment, the acid may be sulfuric acid. In a further embodiment, the acid may be hydrofluoric acid. However, it should be understood that other acids, such as organic acids including, but not limited to, acetic acid, propionic acid, etc. may also be utilized. The acid may be provided before the third solvent in one embodiment. In another embodiment, the acid may be provided with the third solvent. In a further embodiment the acid may be provided with the third solvent.

[0092] The amount of acid utilized may be selectively controlled in order to minimize or prevent any conversion of the salt of the multi-ring disalicylate compound to the free acid form of the multi-ring disalicylate compound in order to render it generally insoluble in the third solvent. In this regard, the amount of acid utilized may be initially controlled to convert any salt of the multi-ring aromatic alcohol to the multi-ring aromatic alcohol for selective dissolution in the third solvent, such as the good solvent for the multi-ring aromatic alcohol and the poor solvent for the salt of the multi-ring disalicylate compound. The approximate amount of acid necessary may be determined by one skilled in the art based on the amount of reagents initially utilized and the use of chromatography, such as HPLC, on the crude mixture to determine an approximate amount of the salt of the multi-ring aromatic alcohol present within the mixture.

[0093] After the above purification steps, if the multi-ring disalicylate compound or salt thereof is present in a dissolved state, solid-liquid separation as generally known in the art may be performed by conventional means to remove any undissolved components from a respective mixture. For instance, these means may be those generally known in the art of liquid-solid separations, such as filtration. However, if the multi-ring disalicylate compound or salt thereof is present in an undissolved state, such solid-liquid separation techniques may not be utilized to remove undissolved components but may be utilized to remove any liquid present if desired.

[0094] Upon purification, particularly washing, the purified product mixture may be acidified to form the multi-ring disalicylate compound. However, it should be understood that in certain embodiments, the reaction product mixture may not be purified. In this regard, the reaction product mixture may be acidified to form the multi-ring disalicylate compound. Accordingly, such acidification may occur prior to any purification of the reaction product mixture as defined herein.

[0095] Nevertheless, such acidification may provide a product mixture, in particular an acidified product mixture, comprising the multi-ring disalicylate compound. In this regard, the method may also include a step of adding an acid to the respective product mixture, such as the purified product mixture or the reaction product mixture. The acid may be a mineral acid in one embodiment. In another embodiment, the acid may be an oxoacid. In a further embodiment, the acid may be a strong acid. The acid may be sulfuric acid, hydrochloric acid, hydrofluoric acid, nitric acid, phosphoric acid, perchloric acid, etc. In one embodiment, the acid may be hydrochloric acid. In another embodiment, the acid may be sulfuric acid. In a further embodiment, the acid may be hydrofluoric acid. However, it should be understood that other acids, such as organic acids including, but not limited to, acetic acid, propionic acid, etc. may also be utilized. The acid may be provided with water such that a mixture is provided.

[0096] Regardless of the type of acid, the desired pH within the respective product mixture may be 6 or less, such as 5 or less, such as 4 or less, such as 3 or less, such as 2 or less to 1 or more, such as 2 or more, such as 3 or more, such as 4 or more.

[0097] In addition, such acidification may be conducted using a particular concentration of the acid. In this regard, the concentration of the acid is not necessarily limited by the present disclosure so long as the acidification assists in converting the salt of the multi-ring disalicylate compound to the multi-ring disalicylate compound. In this regard, such acid (or concentrated acid) may be provided with a liquid, such as water.

[0098] In general, it should be understood that such acidification may be at least partial acidification. For instance, the acidification may be at least partial acidification or even complete acidification.

[0099] The product mixture, such as after acidification, may undergo further separation steps and / or purification steps to obtain the final product mixture. For instance, in one embodiment, the product mixture may undergo one or more further separation steps. In another embodiment, the product mixture may undergo one or more further purification steps. In a further embodiment, the product mixture may undergo further separation steps and further purification steps. These separation steps and purification steps may be those as defined above.

[0100] For instance, in one embodiment, the product mixture may be subjected to a further separation step. In this regard, the method may include a step of removing the product mixture from the liquid to provide a product mixture residue. Such removal may be performed by conventional means. For instance, these means may be those generally known in the art of liquid-solid separations, such as filtration.

[0101] Further, the product mixture before any separation or a product mixture residue as mentioned above may be washed. For instance, it may be washed with water, such as deionized water, and / or an organic compound such as those mentioned above.

[0102] In one embodiment, the product mixture and / or the product mixture residue including the multi-ring disalicylate compound may be dried to form a final product mixture. For instance, it may be dried after purification and / or separation as mentioned above. If the method does not include a purification step, the respective product mixture or product mixture residue as mentioned above may be dried.

[0103] Regardless, the drying may be conducted using means generally known in the art, such as in an oven. Drying may be conducted under normal pressure or under reduced pressure, such as by using a vacuum oven. Also, the drying may be conducted at a temperature greater than room temperature, such as 20°C or more, such as 30°C or more, such as 40°C or more, such as 50°C or more, such as 60°C or more, such as 70°C or more, such as 80°C or more, such as 90°C or more. The drying may be conducted at a temperature of 150°C or less, such as 130°C or less, such as 120°C or less, such as 110°C or less, such as 100°C or less, such as 90°C or less, such as 80°C or less.

[0104] The final product mixture may have a relatively low alkali content. For instance, the final product mixture may have an alkali content of 5000 ppm or less, such as 4000 ppm or less, such as 3000 ppm or less, such as 2000 ppm or less, such as 1000 ppm or less, such as 800 ppm or less, such as 600 ppm or less, such as 500 ppm or less, such as 400 ppm or less, such as 300 ppm or less, such as 200 ppm or less, such as 100 ppm or less.

[0105] The final product mixture may include the multi-ring disalicylate compound in an amount of about 50 wt.% or more, such as about 60 wt.% or more, such as about 70 wt.% or more, such as about 75 wt.% or more, such as about 80 wt.% or more, such as about 85 wt.% or more, such as about 90 wt.% or more, such as about 93 wt.% or more, such as about 95 wt.% or more, such as about 96 wt.% or more, such as about 97 wt.% or more, such as about 98 wt.% or more, such as about 99 wt.% or more based on the weight of the final product mixture.

[0106] The final product mixture may have an impurity content of 40 wt.% or less, such as 35 wt.% or less, such as 30 wt.% or less, such as 25 wt.% or less, such as 20 wt.% or less, such as 18 wt.% or less, such as 15 wt.% or less, such as 13 wt.% or less, such as 10 wt.% or less, such as 8 wt.% or less, such as 6 wt.% or less, such as 4 wt.% or less, such as 3 wt.% or less, such as 2 wt.% or less, such as 1 wt.% or less based on the weight of the final product mixture. These impurities may include other components, such as residual solvents, raw materials, by-products, etc. other than the multi-ring disalicylate compound.

[0107] As indicated herein, the final product mixture comprises the multi-ring disalicylate compound, which as indicated in the structures below is a dicarboxylated disalicylate compound. However, the final product mixture may contain a multi-ring aromatic alcohol that has only undergone a monocarboxylation rather than a dicarboxylation. In this regard, the compound may not be fully dicarboxylated and may only include one carboxyl substituent group. In this regard, such compound will be referred to as a monocarboxylated compound. The final product mixture may have a monocarboxylated compound impurity content of 40 wt.% or less, such as 35 wt.% or less, such as 30 wt.% or less, such as 25 wt.% or less, such as 20 wt.% or less, such as 18 wt.% or less, such as 15 wt.% or less, such as 13 wt.% or less, such as 10 wt.% or less, such as 8 wt.% or less,such as 6 wt.% or less, such as 4 wt.% or less, such as 3 wt.% or less, such as 2 wt.% or less, such as 1 wt.% or less based on the weight of the final product mixture.

[0108] In addition, as indicated in the structures below, a desired product is a dicarboxylated disalicylate compound. However, the final product mixture may contain a multi-ring aromatic mono-carbonic acid ester salt over a phenolate group as shown in the structure belowwhereinM is an alkali metal as defined herein.

[0109] In this regard, such compound will be referred to as a monocarbonic acid ester salt. The final product mixture may have a mono-carbonic acid ester salt impurity content of 40 wt.% or less, such as 35 wt.% or less, such as 30 wt.% or less, such as 25 wt.% or less, such as 20 wt.% or less, such as 18 wt.% or less, such as 15 wt.% or less, such as 13 wt.% or less, such as 10 wt.% or less, such as 8 wt.% or less, such as 6 wt.% or less, such as 4 wt.% or less, such as 3 wt.% or less, such as 2 wt.% or less, such as 1 wt.% or less based on the weight of the final product mixture.

[0110] a. Multi-Ring Aromatic Alcohol or Salt of a Multi-RingAromatic Alcohol

[0111] As indicated above, the first reagent mixture includes a multi-ring aromatic alcohol. In general, the multi-ring aromatic alcohol can correspond to a multi-ring aromatic compound that includes at least two hydroxyl (-OH) groups attached to the carbons in the aromatic rings within the compound. In some embodiments, carbon atoms in at least two different aromatic rings in a multi-ring aromatic alcohol can correspond to carbon atoms that are attached to a hydroxyl group.

[0112] In addition, the term “multi-ring” may refer to compounds that include two or more ring structures (i.e., cyclic structures). The rings can correspond to fused rings, such as a naphthalene-type structure, rings bonded together without sharing an atom, such as a biphenyl linkage, or rings separated by one or more atoms, such as rings separated by a methyl linkage. A multi-ring compound can include multiple aromatic rings, multiple non-aromatic rings (such as saturated rings and / or rings including an insufficient number of double bonds to provide aromaticity), or a combination thereof. Under this definition, rings within a fused ring structure are counted as separate rings, so naphthalene is defined as a compound that includes two aromatic rings.

[0113] In one embodiment, the multi-ring aromatic alcohol includes multiple aromatic rings. For instance, such rings may be bonded together without sharing an atom.

[0114] In one embodiment, the aromatic rings in a multi-ring aromatic alcohol can include only carbon atoms, so that “heteroatoms” such as nitrogen or oxygen are not present in the aromatic rings of the multi-ring aromatic alcohol.

[0115] Further, the multi-ring aromatic alcohol can be selected so that the relative location of the alcohol groups in the multi-ring aromatic alcohol matches the location of the hydroxyl group portions of the salicylate groups in the desired or target multi-ring disalicylate compound. Further, at least one “ortho” location on the multi-ring aromatic alcohol relative to each hydroxyl group also needs to be available to allow for the addition of a CO2 to form the carboxylate group. In some embodiments, both positions “ortho” to each hydroxyl group are available. In this regard, the multi-ring aromatic alcohol comprises at least one hydroxyl group bonded to a carbon in an aromatic ring wherein each carbon atom in an ortho position in the aromatic ring is bonded to a hydrogen in one embodiment.

[0116] The multi-ring aromatic alcohol may include, but is not limited to, a dihydroxynaphthalene (e.g., 1 ,4-dihydroxynaphthalene, 1 ,5-dihydroxynaphthalene, 1 ,6-dihydroxynaphthalene), a biphenol (e.g., 4,4’-biphenol, 2,2’-biphenol), a dihydroxyanthracene (e.g., 2,6-dihydroxyanthracene), etc. In one embodiment, the multi-ring aromatic alcohol may be a dihydroxynaphthalene. In another embodiment, the multi-ring aromatic alcohol may a biphenol. For instance, thebiphenol may be 4, 4’ -biphenol in one embodiment. In another embodiment, the biphenol may be 2,2’-biphenol.

[0117] By adding a carboxylate group at an ortho position relative to each alcohol group, the resulting multi-ring disalicylate compound can be converted to a dicarboxylated compound. As an example, if the multi-ring aromatic alcohol is 4,4’-biphenol, it can be converted to 4,4'-dihydroxy-[1 , 1 '-biphenyl-3,3'-dicarboxylic acid], which may also be referred to as H4DOBPDC. Further, due to the free rotation around the biphenyl bond and the lack of a chiral center, addition of a carboxylate at either ortho position results in the production of the same compound.

[0118] In addition to the above, it should be understood that other compounds may also be utilized, such as substituted biphenol compounds as well as other types of multi-ring aromatic alcohols.

[0119] Furthermore, as indicated herein, the method may begin with a salt of the multi-ring aromatic alcohol. In this regard, the multi-ring aromatic alcohol may be as mentioned above. The salt may be as mentioned herein. For instance, the salt may be formed from an initial reaction of the multi-ring aromatic alcohol and a base, such as those mentioned herein. In this regard, the salt may be an alkali salt, such as when utilizing an alkali for the base. Furthermore, the salt may be a disalt, such as a dialkali salt, when utilizing an alkali for the base. In particular, the salt may be a sodium salt, such as a disodium salt, in one embodiment. In another embodiment, the salt may be a potassium salt, such as a dipotassium salt. In a further embodiment, the salt may be a lithium salt, such as a dilithium salt.

[0120] b. Base

[0121] As indicated above, the first reagent mixture includes a base. However, as indicated above, the second reagent mixture may also include a base. The base is not generally limited by the present disclosure. For instance, the base may include, but is not limited to, an alkali carbonate, an alkali bicarbonate, an alkali hydroxide, or a mixture thereof. In one embodiment, the base may include an alkali carbonate. In another embodiment, the base may include an alkali bicarbonate. In a further embodiment, the base may include an alkali hydroxide.

[0122] The alkali may include but is not limited to, sodium, potassium, lithium, rubidium, and / or cesium. In one embodiment, the alkali may include sodium. In another embodiment, the alkali may include potassium. In a further embodiment, the alkali may include lithium. In another further embodiment, the alkali may include rubidium. In a further embodiment, the alkali may include cesium.

[0123] Examples of bases may include, but are not limited to, KOH, KHCOs, K2CO3, NaOH, NaHCOs, Na2COs, LiOH, LiHCOs, I 2CO3, and mixtures thereof. For instance, the base may include, but is not limited to, KHCO3, K2CO3, NaOH, and mixtures thereof. In one embodiment, the base may include KOH. In another embodiment, the base may include K2CO3. In a further embodiment, the base may include KHCO3. However, it should be understood that other bases also known in the art may be utilized.

[0124] Further, in one embodiment, the base may be a solid base, such as under ambient conditions.

[0125] In addition, as indicated herein, upon reacting with the base, the multi-ring aromatic alcohol may then become a salt of the multi-ring aromatic alcohol. In particular, the salt may be an alkali salt of the multi-ring aromatic alcohol. Particularly, because the base may react with at least two hydroxyl groups of the multi-ring aromatic alcohol, the salt may be a dialkali salt of the multiring aromatic alcohol.

[0126] In one embodiment, the base may not include an alkali carbonate. In this regard, based on the total amount of the base, an alkali carbonate may be present in an amount of about 5 wt.% or less, such as about 4 wt.% or less, such as about 3 wt.% or less, such as about 2 wt.% or less, such as about 1 wt.% or less, such as about 0.5 wt.% or less, such as about 0.3 wt.% or less, such as about 0.1 wt.% or less, such as about 0.05 wt.% or less, such as about 0.01 wt.% or less, such as about 0.005 wt.% or less, such as about 0 wt.%.

[0127] Furthermore, such aforementioned weight percentages may apply to any respective alkali carbonate mentioned herein.

[0128] In one embodiment, the base may not include an alkali bicarbonate. In this regard, based on the total amount of the base, an alkali bicarbonate may be present in an amount of about 5 wt.% or less, such as about 4 wt.% or less, suchas about 3 wt.% or less, such as about 2 wt.% or less, such as about 1 wt.% or less, such as about 0.5 wt.% or less, such as about 0.3 wt.% or less, such as about 0.1 wt.% or less, such as about 0.05 wt.% or less, such as about 0.01 wt.% or less, such as about 0.005 wt.% or less, such as about 0 wt.%.

[0129] Furthermore, such aforementioned weight percentages may apply to any respective alkali bicarbonate mentioned herein.

[0130] c. Solvent

[0131] As indicated above, the respective reagent mixture or intermediate mixture may include a solvent. For instance, the first reagent mixture may optionally include a first solvent. In one embodiment, the first reagent mixture includes a first solvent. Furthermore, as indicated above, in one embodiment, the second intermediate mixture and / or second reagent mixture may also include a second solvent. Such solvents are not necessarily limited and may include those generally known in the art. In one embodiment, the first solvent may be a nonaqueous solvent. In one embodiment, the second solvent may be a non-aqueous solvent.

[0132] Depending on the respective reagent mixture, the respective reagent, and the respective solvent, dissolution or suspension may occur. For instance, a respective solvent may be utilized to suspend any one or more reagents. Alternatively, a respective solvent may be utilized to dissolve any one or more reagents. As an example, a first solvent may be utilized to first suspend the multiring aromatic alcohol. The first solvent may also be utilized to dissolve the base. Further, depending on the temperature, the first solvent may also be utilized to dissolve the multi-ring aromatic alcohol. Also, the second solvent may be utilized to form a suspension with the salt of the multi-ring aromatic alcohol. In another embodiment, the second solvent may be utilized to dissolve the salt of the multiring aromatic alcohol. In this regard, such dissolution may result in a solution rather than a suspension. Then, appropriate steps may be taken to precipitate the salt from the solution. Alternatively, appropriate steps may be taken to react the solution with CO2 to form the multi-ring disalicylate compound and / or a salt thereof.

[0133] The first solvent and the second solvent may be the same in one embodiment. In another embodiment, the first solvent and the second solvent may be different.

[0134] The solvent, whether the first solvent and / or the second solvent, may include, but is not limited to, an aliphatic alcohol, an aromatic alcohol, an amide solvent, trichlorobenzene, a cyclic ether solvent, a non-cyclic ether solvent, an aromatic ether solvent, a light oil, etc.

[0135] In one embodiment, the solvent, such as the first solvent, may be an aliphatic alcohol, an aromatic alcohol, an amide solvent, etc. For instance, the solvent, such as the first solvent, may be an aliphatic alcohol in one embodiment. In another embodiment, the solvent, such as the first solvent, may be an amide solvent. In a further embodiment, the solvent, such as the first solvent, may be an aromatic alcohol.

[0136] In one embodiment, the solvent may be an aliphatic alcohol. For instance, the aliphatic alcohol may be an alkyl alcohol wherein the alkyl has from 1 to 10 carbon atoms. For instance, the alkyl may have 10 or less, such as 8 or less, such as 6 or less, such as 4 or less, such as 3 or less, such as 2 or less, such as 1 carbon atom. In this regard, the first solvent may include, but is not limited to, methanol, ethanol, propanol (e.g., n-propanol, isopropanol), butanol (e.g., n- butanol, sec-butanol, isobutanol, tert-butanol), hexanol (e.g., 2-ethylhexanol), ethylene glycol, etc. In one embodiment, the first solvent may include methanol.

[0137] In one embodiment, the aliphatic alcohol may be cyclic. In another embodiment, the aliphatic alcohol may be linear. In a further embodiment, the aliphatic alcohol may be branched.

[0138] In one embodiment, the aliphatic alcohol may have more than one hydroxyl group. For instance, the aliphatic alcohol may have two or more hydroxyl groups. In this regard, in one embodiment, the solvent, such as the aliphatic alcohol, may be glycerol.

[0139] In one embodiment, the solvent may be an amide solvent. The amide solvent may be represented by the following formula:whereinRi is H or-(CH2)n-CH3,R2is - (CH2)m- CH3,R3is -(CH2)P-CH3, and n, m, and p are each independently an integer from 0 to 20.

[0140] Examples of amide solvents are represented by the following formulae:

[0141] In this regard, the amide solvent may include, but is not limited to, N,N-dimethylformamide (DMF), N,N-dimethylacetamide (DMAc), N,N- diethylformamide (DEF), N,N-dibutylformamide, etc. In one embodiment, the amide solvent may be N,N-dimethylformamide (DMF).

[0142] In one embodiment, the solvent may be an aromatic alcohol. Such aromatic alcohols may include a hydroxyl group indirectly bonded to an aromatic carbon. For instance, the aromatic alcohol may include benzyl alcohol, phenethyl alcohol, etc. In one embodiment, the aromatic alcohol may include benzyl alcohol.

[0143] In one embodiment, the solvent, such as the second solvent, may be an aliphatic alcohol, an amide solvent, trichlorobenzene, a cyclic ether solvent, a non-cyclic ether solvent, an aromatic ether solvent, a light oil, etc. For instance, the solvent, such as the second solvent, may be a cyclic ether solvent in one embodiment. In another embodiment, the solvent, such as the second solvent, may be an amide solvent, such as mentioned above. In a further embodiment, the solvent, such as the second solvent, may be trichlorobenzene. In an even further embodiment, the solvent, such as the second solvent, may be a light oil. In another further embodiment, the solvent, such as the second solvent, may be an aliphatic alcohol such as that mentioned above.

[0144] In one embodiment, the solvent, such as the second solvent, may be a cyclic ether solvent. For instance, the cyclic ether solvent may be dioxane, isosorbide dimethyl ether, or a mixture thereof. In one embodiment, the cyclic ether solvent may be dioxane. In another embodiment, the cyclic ether solvent may be isosorbide dimethyl ether.

[0145] In another further embodiment, the solvent, such as the second solvent, may be a non-cyclic ether solvent, an aromatic ether solvent, etc. or a mixture thereof. In this regard, the solvent, such as the second solvent, may be an aromatic ether solvent in one embodiment. In another embodiment, the solvent, such as the second solvent, may be a non-cyclic ether solvent. In other words, the solvent, such as the second solvent, may be a non-cyclic aliphatic ether solvent, an aromatic ether solvent, or a mixture thereof. For instance, the solvent, such as the second solvent, may not be a dioxane. Instead, the solvent, such as the second solvent, may be other types of ether solvents.

[0146] In one embodiment, the second solvent may be a non-cyclic ether solvent. These may include, but are not limited to, ethylene glycol monobutyl ether, diethylene glycol dibutyl ether, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, bis(2-methoxyethyl) ether, tert-amyl ethyl ether, di-tert-butyl ether, di(propylene glycol) methyl ether, propylene glycol methyl ether, dibutyl ether, 2-(2-methoxyethoxy)ethanol, 2-butoxyethanol, etc. as well as mixtures thereof. In one embodiment, such solvent may be a dialkylene glycol dialkyl ether, such as a diethylene glycol dialkyl ether. The second solvent may include, but is not limited to, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, etc. as well as mixtures thereof. In one particular embodiment, the second solvent may be diethylene glycol dibutyl ether.

[0147] In another embodiment, the second solvent may be an aromatic ether solvent. These may include, but are not limited to, diphenyl ether, anisole, etc. In one embodiment, the second solvent may be diphenyl ether. In another embodiment, the second solvent may be anisole.

[0148] Without intending to be limited, it may be observed that certain solvents may unexpectedly allow for a reduced reaction time. For example only, it was found that the use of at least isosorbide dimethyl ether may result in a shorter reaction time than other solvents.

[0149] In one embodiment, the solvent may not include a cyclic ether solvent. For instance, in one embodiment, the first solvent may not include a cyclic ether solvent. In one embodiment, the second solvent may not include a cyclic ether solvent. In this regard, based on the total amount of the solvent, whether the first solvent and / or the second solvent, the cyclic ether solvent may be present inan amount of about 5 wt.% or less, such as about 4 wt.% or less, such as about 3 wt.% or less, such as about 2 wt.% or less, such as about 1 wt.% or less, such as about 0.5 wt.% or less, such as about 0.3 wt.% or less, such as about 0.1 wt.% or less, such as about 0.05 wt.% or less, such as about 0.01 wt.% or less, such as about 0.005 wt.% or less, such as about 0 wt.%.

[0150] In one embodiment, the solvent may not include dioxane. For instance, in one embodiment, the first solvent may not include dioxane. In one embodiment, the second solvent may not include dioxane. In this regard, based on the total amount of the solvent, whether the first solvent and / or the second solvent, dioxane may be present in an amount of about 5 wt.% or less, such as about 4 wt.% or less, such as about 3 wt.% or less, such as about 2 wt.% or less, such as about 1 wt.% or less, such as about 0.5 wt.% or less, such as about 0.3 wt.% or less, such as about 0.1 wt.% or less, such as about 0.05 wt.% or less, such as about 0.01 wt.% or less, such as about 0.005 wt.% or less, such as about 0 wt.%.

[0151] In one embodiment, the solvent may not include an amide solvent, such as the amine solvent as defined herein. For instance, in one embodiment, the first solvent may not include an amide solvent. In one embodiment, the second solvent may not include an amide solvent. In this regard, based on the total amount of the solvent, whether the first solvent and / or the second solvent, the amide solvent may be present in an amount of about 5 wt.% or less, such as about 4 wt.% or less, such as about 3 wt.% or less, such as about 2 wt.% or less, such as about 1 wt.% or less, such as about 0.5 wt.% or less, such as about 0.3 wt.% or less, such as about 0.1 wt.% or less, such as about 0.05 wt.% or less, such as about 0.01 wt.% or less, such as about 0.005 wt.% or less, such as about 0 wt.%.

[0152] In one embodiment, the solvent may not include an aliphatic alcohol solvent having more than 4 carbon atoms. For instance, in one embodiment, the first solvent may not include such an aliphatic alcohol solvent having more than 4 carbon atoms. In one embodiment, the second solvent may not include such an aliphatic alcohol solvent having more than 4 carbon atoms. In this regard, based on the total amount of the solvent, whether the first solvent and / or the second solvent, the aliphatic alcohol solvent having more than 4 carbon atoms may be present in an amount of about 5 wt.% or less, such as about 4 wt.% or less, suchas about 3 wt.% or less, such as about 2 wt.% or less, such as about 1 wt.% or less, such as about 0.5 wt.% or less, such as about 0.3 wt.% or less, such as about 0.1 wt.% or less, such as about 0.05 wt.% or less, such as about 0.01 wt.% or less, such as about 0.005 wt.% or less, such as about 0 wt.%.

[0153] In one embodiment, the solvent may not include a hexanol. For instance, in one embodiment, the first solvent may not include a hexanol. In one embodiment, the second solvent may not include a hexanol. In this regard, based on the total amount of the solvent, whether the first solvent and / or the second solvent, a hexanol may be present in an amount of about 5 wt.% or less, such as about 4 wt.% or less, such as about 3 wt.% or less, such as about 2 wt.% or less, such as about 1 wt.% or less, such as about 0.5 wt.% or less, such as about 0.3 wt.% or less, such as about 0.1 wt.% or less, such as about 0.05 wt.% or less, such as about 0.01 wt.% or less, such as about 0.005 wt.% or less, such as about 0 wt.%.

[0154] In one embodiment, the solvent may not include 2-ethylhexanol. For instance, in one embodiment, the first solvent may not include 2-ethylhexanol. In one embodiment, the second solvent may not include 2-ethylhexanol. In this regard, based on the total amount of the solvent, whether the first solvent and / or the second solvent, 2-ethylhexanol may be present in an amount of about 5 wt.% or less, such as about 4 wt.% or less, such as about 3 wt.% or less, such as about 2 wt.% or less, such as about 1 wt.% or less, such as about 0.5 wt.% or less, such as about 0.3 wt.% or less, such as about 0.1 wt.% or less, such as about 0.05 wt.% or less, such as about 0.01 wt.% or less, such as about 0.005 wt.% or less, such as about 0 wt.%.

[0155] In one embodiment, the solvent may not include a light oil. For instance, in one embodiment, the first solvent may not include a light oil. In one embodiment, the second solvent may not include a light oil. In this regard, based on the total amount of the solvent, whether the first solvent and / or the second solvent, a light oil may be present in an amount of about 5 wt.% or less, such as about 4 wt.% or less, such as about 3 wt.% or less, such as about 2 wt.% or less, such as about 1 wt.% or less, such as about 0.5 wt.% or less, such as about 0.3 wt.% or less, such as about 0.1 wt.% or less, such as about 0.05 wt.% or less,such as about 0.01 wt.% or less, such as about 0.005 wt.% or less, such as about 0 wt.%.

[0156] The solvent may have a molecular weight of about 50 g / mol or more, such as about 70 g / mol or more, such as about 90 g / mol or more, such as about 110 g / mol or more, such as about 130 g / mol or more, such as about 150 g / mol or more, such as about 170 g / mol or more, such as about 190 g / mol or more, such as about 210 g / mol or more. The molecular weight may be about 500 g / mol or less, such as about 460 g / mol or less, such as about 420 g / mol or less, such as about 380 g / mol or less, such as about 340 g / mol or less, such as about 300 g / mol or less, such as about 280 g / mol or less, such as about 260 g / mol or less, such as about 240 g / mol or less, such as about 220 g / mol or less.

[0157] d. Multi-Ring Disalicylate Compound

[0158] As indicated herein, the method is utilized to make a multi-ring disalicylate compound. In this regard and as generally known in the art, a disalicylate compound corresponds to a compound that includes two monohydroxybenzoate groups.

[0159] In this regard, in one embodiment, the multi-ring disalicylate compound may include:whereinRi is connected to Ri’ and R2 is connected to R2’.

[0160] As indicated above, Ri is connected to Ri’ and R2 is connected to R2’. In general, it should be understood that the connections may not be direct connections. For instance, there may be intermediate atoms / linkages to connect such respective groups.

[0161] In this regard, examples of such multi-ring disalicylate compounds may include, but are not limited to:whereinR is any molecular fragment or a direct linkage.

[0162] In one particular embodiment, the multi-ring disalicylate compound may be:whereinR is any molecular fragment or a direct linkage.

[0163] As indicated above, R is any molecular fragment or a direct linkage.In one embodiment, R is a direct linkage. In another embodiment, R is a molecular fragment as defined below, such as with respect to R17.

[0164] In this regard, when R is a direct linkage, in certain embodiments, the multi-ring disalicylate compound may include two phenyl rings joined at carbon 1 ,1' (i.e. , a biphenyl type linkage), with carboxylic acids on carbons 3,3', and alcohols on carbons 4,4'. This compound can be referred to as “H4DOBPDC” as provided below:(H4DOBPDC)

[0165] Other examples of multi-ring disalicylate compounds can include para-carboxylate (“pc-linker”) such as 4,4'- dioxidobiphenyl-3,3'-dicarboxylate (DOBPDC); 4,4"-dioxido-[1 ,1':4',4"-terphenyl]-3,3"-dicarboxylate (DOTPDC); and dioxidobiphenyl-4,4'-dicarboxylate (para-carboxylate-DOBPDC also referred to as PC-DOBPDC) as well as the following compounds:(H4DOBPDC-X) whereinX is F, Cl, Br, or I.

[0166] In one embodiment, the multi-ring disalicylate compound may have the formula:whereinR11 , R12, R13, R14, R15, and R are each independently hydrogen, halogen, hydroxyl, methyl, and halogen substituted methyl.

[0167] In one embodiment, the multi-ring disalicylate compound may have the formula:whereinR11 , R12, R13, RU, R15, and R are each independently hydrogen, halogen, hydroxyl, methyl, and halogen substituted methyl; andR17 is substituted or unsubstituted aryl, vinyl, alkynyl, substituted or unsubstituted heteroaryl, or a combination thereof.

[0168] In one embodiment, the multi-ring disalicylate compound may have the formula:whereinR11 , R12, R13, RU, R15, and R are each independently hydrogen, halogen, hydroxyl, methyl, and halogen substituted methyl.

[0169] In one embodiment, the multi-ring disalicylate compound may have the formula:whereinR11 , R12, R13, U, R15, and R are each independently hydrogen, halogen, hydroxyl, methyl, and halogen substituted methyl.

[0170] As indicated above, Ru, R12, R13, R14, R15, and Rie are each independently hydrogen, halogen, hydroxyl, methyl, and halogen substituted methyl.

[0171] In this regard, R11 may be hydrogen, halogen, hydroxyl, methyl, or halogen substituted methyl. In one embodiment, Ru may be hydrogen. In another embodiment, Ru may be halogen. In a further embodiment, R11 may be hydroxyl. In another further embodiment, R11 may be methyl. In an even further embodiment, Ru may be halogen substituted methyl.

[0172] Further, R12 may be hydrogen, halogen, hydroxyl, methyl, or halogen substituted methyl. In one embodiment, R12 may be hydrogen. In another embodiment, R12 may be halogen. In a further embodiment, R12 may be hydroxyl. In another further embodiment, R12 may be methyl. In an even further embodiment, R12 may be halogen substituted methyl.

[0173] In addition, R13 may be hydrogen, halogen, hydroxyl, methyl, or halogen substituted methyl. In one embodiment, R13 may be hydrogen. In another embodiment, R13 may be halogen. In a further embodiment, R13 may be hydroxyl. In another further embodiment, R13 may be methyl. In an even further embodiment, R13 may be halogen substituted methyl.

[0174] Further, R14 may be hydrogen, halogen, hydroxyl, methyl, or halogen substituted methyl. In one embodiment, R14 may be hydrogen. In another embodiment, R14 may be halogen. In a further embodiment, R14 may be hydroxyl.In another further embodiment, R14 may be methyl. In an even further embodiment, R14 may be halogen substituted methyl.

[0175] In addition, R15 may be hydrogen, halogen, hydroxyl, methyl, or halogen substituted methyl. In one embodiment, R15 may be hydrogen. In another embodiment, R15 may be halogen. In a further embodiment, R15 may be hydroxyl. In another further embodiment, R15 may be methyl. In an even further embodiment, R15 may be halogen substituted methyl.

[0176] Further, R16 may be hydrogen, halogen, hydroxyl, methyl, or halogen substituted methyl. In one embodiment, Rie may be hydrogen. In another embodiment, R16 may be halogen. In a further embodiment, R16 may be hydroxyl. In another further embodiment, R16 may be methyl. In an even further embodiment, R may be halogen substituted methyl.

[0177] In addition, as indicated above, R17 is substituted or unsubstituted aryl, vinyl, alkynyl, substituted or unsubstituted heteroaryl, or a combination thereof. Such substituent may also correspond to the “R” molecular fragment defined herein as well. In this regard, R17 (or R) may be substituted or unsubstituted aryl in one embodiment. In another embodiment, R17 (or R) may be vinyl. In a further embodiment, R17 (or R) may be alkynyl. In another further embodiment, R17 (or R) may be substituted or unsubstituted heteroaryl. Such aryl or heteroaryl groups may include multiple bridged aryl or heteroaryl species such as molecules having two (or more) phenyl rings or two phenyl rings joined by a vinyl or alkynyl group.

[0178] In one particular embodiment, the reaction scheme may be as follows:For instance, the reaction and method may include a method of preparing the compound represented by Formula 1 by reacting the compound represented by Formula 2 with a base. The reaction may also include the use of CO2 for carboxylation in one embodiment.

[0179] Related, in another particular embodiment, the reaction scheme may begin with the salt of the multi-ring aromatic alcohol. In this regard, the reaction scheme may be as follows:For instance, the reaction and method may include a method of preparing the compound represented by Formula 1 by reacting the salt compound, in particular the dialkali salt compound, represented by Formula 3, wherein M represents an alkali metal as defined herein, with CO2.

[0180] Related, in another particular embodiment, the reaction scheme may begin with the salt of the multi-ring disalicylate compound. In this regard, the reaction scheme may be as follows:For instance, the reaction and method may include a method of preparing the compound represented by Formula 1 by acidying the salt compound, in particular the dialkali salt compound, represented by Formula 4, wherein M represents an alkali metal as defined herein, such as with an acid.

[0181] Furthermore, while certain above embodiments may primarily correspond to structures wherein two or more aromatic rings are joined via a biphenyl linkage or a molecular fragment / Ri? linker, it should be understood that other multi-ring disalicylate compounds may also be obtained according to the present disclosure. For instance, these compounds may include an aromatic core of two or more fused aromatic rings.

[0182] In addition, the above disclosure references the formation of a salt of the multi-ring disalicylate compound. As indicated herein, such salts may be formed due to the presence of an alkali, such as a base as defined herein. In this regard, for such salts, the aforementioned multi-ring disalicylate compounds mayhave a -C(O)OM substituent rather than a -C(O)OH substituent wherein M refers to an alkali metal as defined herein. For instance, the salt of the multi-ring disalicylate compound may have the following structure:whereinM is an alkali metal as defined herein.

[0183] In this regard, in one embodiment, the desired product may be the salt of the multi-ring disalicylate compound. In this regard, a product mixture containing such salt of the multi-ring disalicylate compound may include the salt of the multi-ring disalicylate compound in an amount of about 50 wt.% or more, such as about 60 wt.% or more, such as about 70 wt.% or more, such as about 75 wt.% or more, such as about 80 wt.% or more, such as about 85 wt.% or more, such as about 90 wt.% or more, such as about 93 wt.% or more, such as about 95 wt.% or more, such as about 96 wt.% or more, such as about 97 wt.% or more, such as about 98 wt.% or more, such as about 99 wt.% or more based on the weight of the product mixture.

[0184] The respective product mixture may have an impurity content of 40 wt.% or less, such as 35 wt.% or less, such as 30 wt.% or less, such as 25 wt.% or less, such as 20 wt.% or less, such as 18 wt.% or less, such as 15 wt.% or less, such as 13 wt.% or less, such as 10 wt.% or less, such as 8 wt.% or less, such as 6 wt.% or less, such as 4 wt.% or less, such as 3 wt.% or less, such as 2 wt.% or less, such as 1 wt.% or less based on the weight of the product mixture. These impurities may include other components, such as residual solvents, raw materials, by-products, etc. other than the multi-ring disalicylate compound.

[0185] In addition, such product mixture may comprise a multi-ring aromatic alcohol that has only undergone a monocarboxylation rather than a dicarboxylation. In this regard, the compound may not be fully dicarboxylated andmay only include one carboxyl substituent group. In this regard, such compound will be referred to as a monocarboxylated compound. The respective product mixture may have a monocarboxylated compound impurity content of 40 wt.% or less, such as 35 wt.% or less, such as 30 wt.% or less, such as 25 wt.% or less, such as 20 wt.% or less, such as 18 wt.% or less, such as 15 wt.% or less, such as 13 wt.% or less, such as 10 wt.% or less, such as 8 wt.% or less, such as 6 wt.% or less, such as 4 wt.% or less, such as 3 wt.% or less, such as 2 wt.% or less, such as 1 wt.% or less based on the weight of the product mixture.

[0186] In addition, as indicated in the structures above, a desired product may be a salt of the multi-ring disalicylate compound. However, the product mixture may contain a multi-ring aromatic mono-carbonic acid ester salt over a phenolate group as shown in the structure belowwhereinM is an alkali metal as defined herein.

[0187] In this regard, such compound will be referred to as a mono-carbonic acid ester salt. The respective product mixture may have a mono-carbonic acid ester salt impurity content of 40 wt.% or less, such as 35 wt.% or less, such as 30 wt.% or less, such as 25 wt.% or less, such as 20 wt.% or less, such as 18 wt.% or less, such as 15 wt.% or less, such as 13 wt.% or less, such as 10 wt.% or less, such as 8 wt.% or less, such as 6 wt.% or less, such as 4 wt.% or less, such as 3 wt.% or less, such as 2 wt.% or less, such as 1 wt.% or less based on the weight of the product mixture.

[0188] e. Applications

[0189] The applications for the multi-ring disalicylate compound and / or salt thereof are not limited by the present disclosure. However, as indicated herein, in one particular embodiment, the multi-ring disalicylate compound and / or saltthereof, in particular the multi-ring disalicylate compound, may be utilized in the formation of a metal organic framework. In this regard, the present disclosure may also be directed to a metal organic framework formed from the multi-ring disalicylate compound and / or salt thereof, in particular the multi-ring disalicylate compound, as disclosed herein. In addition, the present disclosure may also be directed to a metal organic framework formed from the multi-ring disalicylate compound and / or salt thereof, in particular the multi-ring disalicylate compound, formed according to the method as disclosed herein.

[0190] In general, any method utilized in forming a metal organic framework may be utilized in forming such a framework utilizing the multi-ring disalicylate compound and / or salt thereof, in particular the multi-ring disalicylate compound, as disclosed herein.

[0191] In general, metal organic framework molecules may be utilized to selectively capture gases, such as carbon dioxide. For instance, these gases may be generated from, but are not limited to, refineries, turbines, etc. In addition, the gas may also be naturally existing in air. Accordingly, these metal organic frameworks may be utilized to reduce greenhouse gases. In addition, these metal organic frameworks may be utilized to selectively capture certain gases, such as carbon dioxide, while allowing other gasses to flow through.

[0192] In one embodiment, the metal organic framework may be utilized in post-combustion capture. For instance, gases loaded with carbon dioxide may pass through the metal organic framework which selectively adsorbs the carbon dioxide. In another embodiment, the metal organic framework may be utilized in pre-combustion capture. For instance, metal organic frameworks may selectively capture carbon dioxide from syngas for further synthesis use and combustion. In a further embodiment, the metal organic framework may be utilized in direct air capture wherein carbon dioxide is extracted directly from the ambient air.

[0193] Once the gas, such as carbon dioxide, is adsorbed to the metal organic framework, it may be released. For instance, upon heating the metal organic framework, the carbon dioxide may be released and captured into a storage compartment, such as a tank. Such gas, such as carbon dioxide, may thereafter be recycled and utilized for other purposes, such as chemical reactions.Furthermore, due to release of the gas, such as carbon dioxide, the metal organic framework may then be reused.Examples Example 1 - Synthesis of H4DOBPDC

[0194] To prepare H4DOBPDC (4,4’-dihydroxy-l,r-biphenyl-3,3’-dicarboxylic acid), 20.04 grams (0.1076 mol) of biphenol were provided into a four-neck flask. Then, 147 grams of methanol were added and the biphenol was suspended at room temperature using a magnetic stir bar. Separately, potassium hydroxide pastils were ground and then 14.27 grams (-12.1 grams of pure potassium hydroxide; -0.2156 mol; note that the KOH had about 10-15 wt.% water) of the ground material were dissolved in 35.5 grams of methanol. Then, 48.47 grams of the KOH solution were added at 18.6°C into the biphenol suspension while stirring at 300 rpm. The mixture was heated to 26.3°C and the biphenol was dissolved.Then, 119.5 grams of diethylene glycol dibutyl ether were added to the flask. The flask was purged under nitrogen and prepared for distillation of the methanol.Within 70 minutes, a majority of the methanol had been distilled. The temperature of the flask was gradually increased and then set to 120°C. After distilling about 80-90 ml of the methanol, the reaction mixture started to become turbid and the dipotassium salt started to precipitate.

[0195] The heating was further increased to drive out all the water from the potassium hydroxide as well as from the mixture. A heat gun was used to heat the upper parts of the flask (where water could condense) to facilitate the removal.The heater was set to a maximum of 230°C and an inner temperature of 227.4°C was reached. The obtained suspension in the solvent was well stirable and could be transferred into the autoclave.

[0196] The atmosphere in the autoclave was exchanged three times with CO2 gas (with a pressure of -75 psi at 25°C). It was then heated to 245°C and maintained for 6.75 hours. As the temperature was below the boiling temperature of the diethylene glycol dibutyl ether, the heating did not significantly contribute to the overall pressure in the autoclave. It was then cooled down and the next day fresh CO2 of -76 psi at 17°C was provided into the reactor. The reaction was continued for another -6.5 hours to 245°C. It was cooled down for the night andthe next day another -75 psi CO2 at 18°C was provided in the autoclave and heated for -5.75 hours to 245°C. Then, a total CO2 pressure of 200 psi at 20°C was provided onto the reaction mass and kept for 4.25 hours at 245°C (maximum pressure of 533 psi at this temperature). On the final day of the reaction, -230 psi of carbon dioxide was provided into the autoclave and heated for another 6 hours to 245°C (maximum pressure of 636 psi at this temperature). In total, the reaction was kept for 29.25 hours at 245°C at the varying carbon dioxide pressures.

[0197] After this time, it was cooled down and the reactor was opened. The crude product mixture was filtered through a Buechner funnel (Whatman 1 filter paper). The wet filter cake weighed 39.17 grams and still contained diethylene glycol dibutyl ether. The wet filter cake was transferred into a flask and suspended in 198 grams of deionized water. It was acidified with 22.0 grams of 34-37% aqueous hydrochloric acid, which resulted in a thick suspension, and 134 grams of deionized water were added. Then, the thick suspension was filtered (Buechner funnel, Whatman 1 filter paper) and washed subsequently with a total of -450 ml of deionized-water. The final drips of washing water at the outlet of the funnel showed a pH of -4-5. Then, the filter cake was taken out and dried in a vacuum oven at 90°C.

[0198] The product was characterized using GC and HPLC. Figure 2 shows an HPLC spectrum of the final product mixture integrated using phenol as an HPLC internal standard. In this figure, the peak after 9.4 minutes indicates a peak for an internal standard phenol. Figure 3 shows an HPLC spectrum of the crude product and phenol which is used as an internal standard and reference point. The spectra indicate that H4DOBPDC was obtained.

[0199] The final analysis of the mixture revealed a crude reaction product, prior to any purification, which still contained 16.47 wt.% of diethylene glycol dibutyl ether (determined per GC). The HPLC (detected at 254 nm) gave a purity of 96.9% (area) dicarboxylated biphenol, 1.61 % (area) biphenol, and 1.47% (area) of an unknown compound before the target (likely the monocarboxylated biphenol). At this wavelength the HPLC did not show the residual diethylene glycol dibutyl ether. The identification of the peaks is based on the retention times provided in the table below.

[0200] Table 1 : HPLC Analysis - Identification of Peak (for Figures 2 and 3)Example 2 - Synthesis of H2K2DOBPDC

[0201] To prepare H2K2DOBPDC (4,4’-dihydroxy-l,r-biphenyl-3,3’- dicarboxylic acid dipotassium salt), 22.92 grams of biphenol were slurried in 207 ml methanol in a 500 ml four neck flask under nitrogen, equipped with a magnetic stirrer and a Dean-Stark trap. To the obtained suspension, a solution of 16.38 grams potassium hydroxide (85%), in 45.65 grams of methanol were added dropwise. Then, 155 ml of diethylene glycol dibutyl ether were added and started to heat to distill out and remove the methanol. After 254 ml of methanolic distillate were removed (pot temperature of 110°C), the apparatus was equipped to vacuum distillation and slowly vacuum was pulled. At a pot temperature of 120°C and a vacuum of 121 Torr, the vacuum was broken and an additional 4.27 g of distillate were removed. Then, the vacuum was resumed, and at 46 Torr and 123.6°C, heavy boiling was observed. It was carefully pulled to the full vacuum of 18 Torr, and a pot temperature of 129.0°C was reached. The final conditions were 133.4°C and 19 Torr. Then, the vacuum was broken and the reaction slurry was transferred into a 450 ml pressure reactor (1.53 grams calculated as biphenol were left in the flask, with 21 .39 grams of biphenol transferred as the potassium salt into the pressure reactor). The reaction mass was put under carbon dioxide (starting carbon dioxide pressure was 234 psi at 18’C), and it was heated at 220°C for seven hours. The reaction was interrupted for the night and the next morning repressurized to the same carbon dioxide pressure and heated to 220°C. This was subsequently repeated two more times so that the reaction mass was for a total of 28 hours at 220°C.

[0202] After this time, the reaction mass was cooled down and the obtained slurry was filtered through a Buechner funnel. The filter cake was washed with a total of 98.7 grams of methy l-tert-butyl ether. The filter cake was dried in a vacuum oven at 90°C at ~18 Torr to give a total of 38.3 grams of dried crudeproduct mixture in the form of its dipotassium salt. The HPLC showed the following HPLC area% for the organic compounds (neglecting the potassium), measured at 254 nm: 2.10% biphenol (10.35 min); 1.52% of mono-ester of carbonic acid with the dicarboxylated biphenol; 2.1 1 % of monocarboxylated biphenol; 94.27% dicarboxylated biphenol (12 min).

[0203] To increase the purity of such crude product mixture in the form of a dipotassium salt, the insolubility of the dipotassium salt of the disalicylate compound was exploited. Biphenol has a pKa of about 9.74 (+ 0.26, theoretical), which is much higher than the pKa of the final dicarboxylated biphenol product, which is 2.72 (+ 0.10). As a result and without intending to be limited, a free proton would first exchange a potassium at the biphenolate before it would go to the potassium salt of the disalicylate compound. The method includes the addition of the appropriate amount of acid to convert the potassium salt of the biphenolate into the free, acetone soluble biphenol without converting the acetone insoluble potassium salt of the disalicylate compound.

[0204] In this regard, 30.29 grams of the crude product mixture were taken up in 197.8 grams of acetone and 2.69 grams of concentrated hydrochloric acid added. It was heated for six hours to reflux and then cooled down. The cool reaction mass was filtered, and, after drying, a total of 29.75 grams purified product mixture was obtained (95.80% (area HPLC @ 254 nm) final product, 0.25% biphenol). The acetone layer was evaporated and the product residue examined by HPLC which initially showed 85.25% (area HPLC @ 254 nm) biphenol, 12.12% monocarboxylated biphenol and only 0.93% in the final product.

[0205] As another example, the same starting material was taken up in the same equivalent of acetone but this time exposed to a relative double amount of concentrated hydrochloric acid. In particular, 4.99 grams of the crude product mixture were taken up in 32.99 grams of acetone and 0.86 grams of concentrated hydrochloric acid and heated to reflux temperature for 3.5 hours. After cooling and work-up, the purified 4.79 grams of product as dipotassium salt had a purity of 96.24% (area HPLC @ 254 nm) and with 1.77% (area HPLC @ 254 nm) less of the monocarboxylated biphenol. Meanwhile, the biphenol area HPLC was 0.23%.Example 3 - Synthesis of H2K2DOBPDC

[0206] To prepare H2K2DOBPDC (4,4’-dihydroxy-l,r-biphenyl-3,3’- dicarboxylic acid), 20.09 grams of biphenol were slurried in 179 ml methanol in a 500 ml four neck flask under nitrogen, equipped with a magnetic stirrer and a Dean-Stark trap. To the obtained suspension, a solution of 14.92 grams potassium hydroxide (85%), in 40.58 grams of methanol were added dropwise to provide a dissolved potassium biphenolate solution in methanol. For transfer, the flask with the KOH solution was rinsed with an additional 8.7 grams of methanol. Then, 159 ml of isosorbide dimethyl ether were added and started to heat to distill out and remove the methanol and subsequently the water.

[0207] When reaching 64.5°C, bubbles were observed in the flask and at 70.5°C the distillation started. When reaching 75°C, the first turbidity appeared, at 81 °C the stirrer was set to 500 rpm, and at 85°C slight foaming was observed. At 96°C, stirring was increased up to 700 rpm. When reaching 98°C, the reactor content was observed to be thicker and the stirrer was set to 1000 rpm. When reaching 113.8°C, a total of 230 ml distillate had been removed from the side arm of the Dean-Stark trap. When reaching 122.7°C in the flask, 2 more ml of distillate were removed from the side arm of the Dean-Stark trap and the nitrogen was exchanged against vacuum.

[0208] The heating was further increased while applying a slight vacuum (650 - 486 Torr). At 134°C, thicker bubbles were observed. At 137.3°C, 3.5 grams of distillate were removed from the side arm of the Dean-Stark trap. The vacuum was further reduced down to 180 Torr, and the flask temperature was increased up to 150.9°C. Then, heavy boiling occurred in the distillate in the side arm and also in the flask. At these conditions, another 1 .6 grams of distillate were removed from the side arm. The vacuum distillation was continued and the upper parts of the flask were heated using a heat gun. The vacuum was further lowered to 42 Torr and a final temperature of ~148°C was reached in the flask. Under these conditions (including the heat gun treatment), another 8.2 grams of distillate were found in the side arm of the Dean-Stark trap. Then, the vacuum was broken and replaced by nitrogen, and the reaction slurry was transferred into a 450 ml pressure reactor. The reactor was sealed tightly and the atmosphere exchanged against carbon dioxide (-230 Torr pressure) three times. The next morning, at room temperature, the carbon dioxide pressure was adjusted to -234 psi and thenit was heated to 227°C. The temperature / carbon dioxide pressure relation while heating up the reaction mass is illustrated in Figure 4. Then, the temperature was maintained at 227°C for four hours and a pressure drop was observed as illustrated in Figure 5.

[0209] The contents were then cooled down to 40°C and the reactor was vented. Then, the reaction mass was filtered through a Buchner funnel with a Whatman 1 filter paper. The remaining reaction mass was transferred with 57 grams of methyl-tert-butyl ether onto the funnel while also washing the filter cake and then the entire reaction mass washed with another 50.9 grams of methyl-tert- butyl ether. Then, the funnel contents were dried in a vacuum oven at ~100°C.

[0210] A sample was taken to determine the chemical composition. The analysis showed 0.13% (HPLC-area @ 254 nm) BP, 2.98% (area, 254 nm) monoester of carbonic acid of the final product, 1 .08% (area, 254 nm) of the monocarboxylated biphenol as well as 95.77% (area, 254 nm) of the desired product. The retention times are as follows: biphenol - 12.4 minutes, mono-ester of carbonic acid of the final product - 14.7 minutes, monocarboxylated biphenol - 15.3 minutes, and desired final product - 17.4 minutes. Figure 6 shows an HPLC spectrum of the final product mixture.

[0211] In this reaction it was found that 4.23 grams of the original 20.09 grams of biphenol could not be transferred into the pressure reactor. This calculates to 15.86 g transferred biphenol (from originally 20.09 grams which equates to 78.94 wt.% transferred material) and gives a theoretical yield of 29.85 grams of the potassium salt. Finally, 29.05 grams of crude potassium salt of the dicarboxylated biphenol were isolated.

[0212] As demonstrated in the above example, when utilizing isosorbide dimethyl ether, the salt of the dicarboxylated biphenol was obtained in a short reaction time and isolated by simple filtration with subsequent washes in high purities. In this regard, such product could be immediately utilized for end use applications, such as for the production of a metal organic framework.

[0213] These and other modifications and variations of the present disclosure may be practiced by those of ordinary skill in the art, without departing from the spirit and scope of the present disclosure. In addition, it should be understood that aspects of the various embodiments may be interchanged both inwhole or in part. Furthermore, those of ordinary skill in the art will appreciate that the foregoing description is by way of example only and is not intended to limit the disclosure so further described in such appended claims.

Claims

Claims1 . A method of making a multi-ring disalicylate compound, the method comprising: providing a first reagent mixture including a multi-ring aromatic alcohol, a base, and optionally a first solvent in a reactor volume; reacting the multi-ring aromatic alcohol and the base to form a first intermediate mixture comprising a salt of the multi-ring aromatic alcohol, water, and the optional first solvent; adding a second solvent to the reactor volume and removing at least partially the water and the optional first solvent from the reactor volume; adding CO2 to the reactor volume; and reacting the salt of the multi-ring aromatic alcohol and the CO2 to form a final product mixture comprising the multi-ring disalicylate compound.

2. The method of claim 1 , wherein a molar ratio of the base to the multiring aromatic alcohol may be 0.1 or more to 10 or less.

3. The method of claim 1 , wherein a molar ratio of the base to the multiring aromatic alcohol may be from 1 or more to 4 or less.

4. The method of claim 1 , wherein the second solvent is added to the reactor volume prior to the removing step.

5. The method of claim 1 , wherein the removing step results in removing at least 70 wt.% or more of the water from the reactor volume.

6. The method of claim 1 , wherein the reacting step with CO2 is conducted at a temperature of at least 100°C to 300°C or less.

7. The method of claim 1 , wherein the reacting step with CO2 is conducted at a total pressure of from 0.1 MPa to 10 MPa in the reactor volume.

8. The method of claim 1 , wherein the reacting step with CO2 is conducted at a total pressure of from 0.1 MPa to 5 MPa in the reactor volume.

9. The method of claim 1 , wherein the reacting step with CO2 is conducted at a CO2 pressure of from 0.1 MPa to 10 MPa.

10. The method of claim 1 , wherein the reacting step with CO2 is conducted at a CO2 pressure of from 0.1 MPa to 5 MPa.

11. The method of claim 1 , wherein the multi-ring aromatic alcohol comprises 4,4’-biphenol.

12. The method of claim 1 , wherein the base comprises an alkali carbonate, an alkali bicarbonate, an alkali hydroxide, or a mixture thereof.

13. The method of claim 1 , wherein the base comprises an alkali hydroxide.

14. The method of claim 1 , wherein the base comprises potassium hydroxide.

15. The method of claim 1 , wherein the first reagent mixture comprises a first solvent.

16. The method of claim 15, wherein the first solvent comprises an aliphatic alcohol, an aromatic alcohol, or an amide solvent.

17. The method of claim 1 , wherein the second solvent comprises an aliphatic alcohol, an amide solvent, trichlorobenzene, a cyclic ether solvent, a non- cyclic ether solvent, an aromatic ether solvent, or a light oil.

18. The method of claim 1 , wherein the second solvent comprises a non- cyclic ether solvent, an aromatic ether solvent, or a mixture thereof.

19. The method of claim 1 , wherein the second solvent comprises a non- cyclic ether solvent.

20. The method of claim 1 , wherein the second solvent comprises diethylene glycol dibutyl ether.

21. The method of claim 1 , wherein the second solvent comprises isosorbide dimethyl ether.

22. The method of claim 1 , wherein the second solvent comprises glycerol.

23. The method of claim 1 , wherein the step of reacting the salt of the multi-ring aromatic alcohol and the CO2 forms a reaction product mixture, the method further comprising separating the second solvent from the reaction product mixture.

24. The method of claim 23, further comprising acidifying the reaction product mixture with an acid to form an acidified product mixture.

25. The method of claim 24, further comprising separating a liquid from the acidified product mixture to provide a product mixture residue.

26. The method of claim 25, further comprising drying the product mixture residue to form the final product mixture.

27. The method of claim 1 , wherein the step of reacting the salt of the multi-ring aromatic alcohol and the CO2 forms a reaction product mixture, wherein the method further comprises purifying the reaction product mixture.

28. The method of claim 27, wherein the purifying is conducted via suspension washing to form a purified product mixture.

29. The method of claim 28, further comprising acidifying the purified product mixture with an acid to form an acidified product mixture.

30. The method of claim 29, further comprising separating a liquid from the acidified product mixture to provide a product mixture residue.

31. The method of claim 30, further comprising drying the product mixture residue to form the final product mixture.

32. The method of claim 27, wherein the purifying is conducted via selective dissolution to form a purified product mixture.

33. The method of claim 27, wherein the purifying includes contacting the reaction product mixture comprising one or more impurities with a third solvent and an acid, wherein the third solvent dissolves the one or more impurities.

34. The method of claim 33, separating the third solvent including the one or more dissolved impurities from the reaction product mixture to form a purified product mixture.

35. The method of claim 34, further comprising acidifying the purified product mixture with an acid to form an acidified product mixture.

36. The method of claim 35, further comprising separating a liquid from the acidified product mixture to provide a product mixture residue.

37. The method of claim 36, further comprising drying the product mixture residue to form the final product mixture.

38. The method of claim 1 , wherein the multi-ring disalicylate compound is the following:(H4DOBPDC).

39. A method of making a multi-ring disalicylate compound, the method comprising: providing a first reagent mixture including a multi-ring aromatic alcohol, a base, and optionally a first solvent in a reactor volume; reacting the multi-ring aromatic alcohol and the base to form a first intermediate mixture comprising a salt of the multi-ring aromatic alcohol, water, and the optional first solvent; adding a second solvent comprising a non-cyclic ether, an aromatic ether, or a mixture thereof to the reactor volume to form a second intermediate mixture; adding CO2 to the reactor volume; and reacting the salt of the multi-ring aromatic alcohol and the CO2 to form a final product mixture comprising the multi-ring disalicylate compound.

40. A method of making a multi-ring disalicylate compound, the method comprising: providing a second reagent mixture including a salt of a multi-ring aromatic alcohol and a second solvent comprising a non-cyclic ether, an aromatic ether, or a mixture thereof in a reactor volume; adding CO2 to the reactor volume; and reacting the salt of the multi-ring aromatic alcohol and the CO2 to form a final product mixture comprising the multi-ring disalicylate compound.

41. A multi-ring disalicylate compound formed according to a method comprising: providing a first reagent mixture including a multi-ring aromatic alcohol, a base, and optionally a first solvent in a reactor volume;reacting the multi-ring aromatic alcohol and the base to form a first intermediate mixture comprising a salt of the multi-ring aromatic alcohol, water, and the optional first solvent; adding a second solvent to the reactor volume and removing at least partially the water and the optional first solvent from the reactor volume; adding CO2 to the reactor volume; and reacting the salt of the multi-ring aromatic alcohol and the CO2 to form a final product mixture comprising a multi-ring disalicylate compound.

42. A method of making a salt of a multi-ring disalicylate compound, the method comprising: providing a first reagent mixture including a multi-ring aromatic alcohol, a base, and optionally a first solvent in a reactor volume; reacting the multi-ring aromatic alcohol and the base to form a first intermediate mixture comprising a salt of the multi-ring aromatic alcohol, water, and the optional first solvent; adding a second solvent to the reactor volume and removing at least partially the water and the optional first solvent from the reactor volume; adding CO2 to the reactor volume; and reacting the salt of the multi-ring aromatic alcohol and the CO2 to form a reaction product mixture comprising the salt of the multi-ring disalicylate compound.

43. A method of making a salt of a multi-ring disalicylate compound, the method comprising: providing a first reagent mixture including a multi-ring aromatic alcohol, a base, and optionally a first solvent in a reactor volume; reacting the multi-ring aromatic alcohol and the base to form a first intermediate mixture comprising a salt of the multi-ring aromatic alcohol, water, and the optional first solvent; adding a second solvent comprising a non-cyclic ether, an aromatic ether, or a mixture thereof to the reactor volume to form a second intermediate mixture; adding CO2 to the reactor volume; andreacting the salt of the multi-ring aromatic alcohol and the CO2 to form a reaction product mixture comprising the salt of the multi-ring disalicylate compound.

44. A method of making a salt of a multi-ring disalicylate compound, the method comprising: providing a second reagent mixture including a salt of a multi-ring aromatic alcohol and a second solvent comprising a non-cyclic ether, an aromatic ether, or a mixture thereof in a reactor volume; adding CO2 to the reactor volume; and reacting the salt of the multi-ring aromatic alcohol and the CO2 to form a reaction product mixture comprising the salt of the multi-ring disalicylate compound.

45. A method of making a multi-ring disalicylate compound, the method comprising: providing a first reagent mixture including a multi-ring aromatic alcohol, a base, and optionally a first solvent in a reactor volume; reacting the multi-ring aromatic alcohol and the base to form a first intermediate mixture comprising a salt of the multi-ring aromatic alcohol, water, and the optional first solvent; adding a second solvent to the reactor volume and optionally removing at least partially the water and the optional first solvent from the reactor volume; adding CO2 to the reactor volume; reacting the salt of the multi-ring aromatic alcohol and the CO2 to form a reaction product mixture comprising a salt of the multi-ring disalicylate compound and one or more impurities; contacting the reaction product mixture with an acid and a third solvent for at least partially dissolving the one or more impurities; separating the third solvent with the dissolved one or more impurities from the reaction product mixture to form a purified product mixture; and acidifying the purified product mixture to form a final product mixture comprising a multi-ring disalicylate compound.

46. A multi-ring disalicylate compound formed according to any preceding claim.

47. A metal organic framework formed from the multi-ring disalicylate compound of claim 46.

48. A multi-ring disalicylate compound formed according to a method comprising: providing a first reagent mixture including a multi-ring aromatic alcohol, a base, and optionally a first solvent in a reactor volume; reacting the multi-ring aromatic alcohol and the base to form a first intermediate mixture comprising a salt of the multi-ring aromatic alcohol, water, and the optional first solvent; adding a second solvent to the reactor volume and optionally removing at least partially the water and the optional first solvent from the reactor volume; adding CO2 to the reactor volume; reacting the salt of the multi-ring aromatic alcohol and the CO2 to form a reaction product mixture comprising a salt of the multi-ring disalicylate compound and one or more impurities; contacting the reaction product mixture with an acid and a third solvent for at least partially dissolving the one or more impurities; separating the third solvent with the dissolved one or more impurities from the reaction product mixture to form a purified product mixture; and acidifying the purified product mixture to form a final product mixture comprising the multi-ring disalicylate compound.

49. A metal organic framework formed from the multi-ring disalicylate compound of claim 48.

Images