A method for producing and / or isolating isoidides, comprising selective esterification of a mixture of dianhydrohexitol isomers.

Abstract

Disclosed herein are methods for producing and / or isolating isoidide, compositions comprising mixtures containing unesterified isoidide and one or both compounds selected from the group consisting of esterified isosorbide and esterified isomannide, and the use of such compositions in methods for producing and / or isolating isoidide. Further disclosed herein is the use of a method comprising the step of selective esterification of a mixture of dianhydrohexitol isomers containing isoidide to separate isoidide from a mixture of dianhydrohexitol isomers. Additionally, disclosed are methods for producing polymers comprising isoidide monomers or modified isoidide monomers.

Description

[Technical Field]

[0001] The present invention relates to a method for producing and / or isolating isoidides, a composition comprising a mixture containing a non-esterified isoidide and one or both compounds selected from the group consisting of esterified isosorbide and esterified isomannide, and the use of such compositions in a method for producing and / or isolating isoidides. The present invention further relates to the use of a method comprising the step of selectively esterifying a mixture of dianhydrohexitol isomers containing isoidides to separate the isoidides from the mixture of dianhydrohexitol isomers. Furthermore, the present invention relates to a method for producing polymers containing isoidide monomers or modified isoidide monomers. [Background technology]

[0002] Dianhydrohexitol, sometimes also called "isohexide," is a bicyclic, oxygen-containing heterocycle formed from two anelate tetrahydrofuran rings. Dianhydrohexitol includes the compounds isosorbide, isomannide, and isoidide. The dianhydrohexitol can be obtained, for example, by double dehydration of the sugar alcohols sorbitol, mannitol, or iditol, each by processes known in the art.

[0003] Isoidides are compounds that have attracted attention for their usefulness in industrial synthesis, for example, as building blocks for polymers derived from renewable and / or biodegradable resources.

[0004] Isosorbide can be produced from D-glucose via D-sorbitol as an intermediate, and isomannide can be produced from D-fructose via D-mannitol as an intermediate; therefore, both isosorbide and isomannide are generally available in industrial quantities without any particular problems. However, iditol, the starting material for the production of isoidide, is not available in technical quantities. Thus, efforts have been made in the past to prepare isoidide in larger quantities, including epimerization methods using isosorbide or isomannide as starting materials.

[0005] The following literature discusses a specific modifier of dianhydrohexitol: Reference US 4,417,065 describes a method for preparing isosorbide 2-nitrate. Document EP 3 056 496 relates to a method for producing isoidides. Reference US 2012 / 116101 discloses a method for preparing dianhydrohexitol diester compositions. Reference US 3,023,223 discusses methods for producing isoidides. Document WO 2013 / 125950 discloses a method for producing isoidides. P. Stoss et al., in Synthesis, 1987, pp. 174-176, reported on the regioselective acylation of 1,4:3,6-dianhydro-D-glucitol. [Overview of the project] [Problems that the invention aims to solve]

[0006] Considering existing prior art, there is still a need for simpler methods for producing and / or isolating isoidides, particularly for methods that produce and / or isolate isoidides with higher efficiency, including higher yields from the isoidide isolation step.

[0007] Accordingly, the main object of the present invention was to provide a simple method for producing and / or isolating isoidides and compositions for use in such a method.

[0008] Another object of the present invention was to provide a method for separating isoidides from a mixture of dianhydrohexitol isomers, including isoidides, by applying a method for selective derivatization of dianhydrohexitol isomers.

[0009] In addition, a more specific object of the present invention was to provide a method for producing polymers containing isoidide monomers or modified isoidide monomers obtained by a simpler method for producing and / or isolating isoidides. [Means for solving the problem]

[0010] The main and other objectives of the present invention are, Formula I

[0011] [ka] A method for producing and / or isolating an isoidide, comprising the following steps: M3) Formula II comprising one or both compounds selected from the group consisting of isoidides, isosorbides, and isomannides.

[0012] [ka] A step of preparing or making a mixture of the compounds, and M4) The step of subjecting the mixture of compounds of formula II from step M3) to selective esterification conditions so that a mixture (or each of them) containing one or both compounds selected from the group consisting of non-esterified isoidides, esterified isosorbides, and esterified isomannides is obtained. It is now known that this can be achieved by methods including [specific methods]. [Modes for carrying out the invention]

[0013] The present invention, its preferred variants, and the preferred combinations of their parameters, characteristics, and elements are defined in the appended claims. The preferred embodiments, details, modifications, and advantages of the present invention are also defined and explained in the following description and the examples shown below.

[0014] The method for producing and / or isolating isoidide according to the present invention is extremely efficient (e.g., in terms of energy consumption and / or cost), and it has now been found that it enables the very simple isolation of isoidide from a mixture containing non-esterified isoidide and esterified dianhydrohexitol isomers under mild conditions and in high yields.

[0015] In particular, it has been found in specific experiments that isoidide (under the conditions of the method for producing and / or isolating isoidide according to the present invention) is esterified, particularly acylated, and particularly acetylated much more slowly than isosorbide or isomannide.

[0016] In the context of the present invention, in accordance with the ordinary meaning in the art, the compound isoidide means a compound also known by the chemical name "1,4:3,6-dianhydro-L-iditol" (CAS RN: 24332-71-6). In the context of the present invention, in accordance with the ordinary meaning in the art, the compound isosorbide means a compound also known by the name "D-isosorbide" or the chemical name "1,4:3,6-dianhydro-D-sorbitol" or "1,4:3,6-dianhydro-D-glucitol" (CAS RN: 652-67-5). In the context of the present invention, in accordance with the ordinary meaning in the art, the compound isomannide means a compound also known by the chemical name "1,4:3,6-dianhydro-D-mannitol" (CAS RN: 641-74-7).

[0017] In the context of the present invention, the terms "isoidide" and "non-esterified isoidide" are used as synonyms.

[0018] In the context of the present invention, the terms “selective esterification” or “stereoselective esterification” mean, in accordance with the common sense in the art, that a non-stereospecific mechanism (here, non-stereospecific esterification) allows for the formation of multiple products (here, monoesters of dianhydrohexitol, diesters of dianhydrohexitol, or unesterified dianhydrohexitol), but that the properties of the reaction mixture (here, a mixture of dianhydrohexitol isomers) are such that the steric approach is favorable to only one (or some) of the products, regardless of the reaction mechanism.

[0019] In the context of the present invention, the terms “esterified isoidide,” “esterified isosorbide,” “esterified isomannide,” and “esterified dianhydrohexitol” all include, in any case, the respective monoesterified (specifically, monoacylated or monoacetylated) compounds, the respective monoesters thereof, and the respective bisesterified (specifically, bisacylated or bisacetylated) compounds, the respective diesters thereof, and the respective mixtures of monoesterified and bisesterified compounds. Depending on the reaction conditions applied to the observed particular dianhydrohexitol and its esterification, monoesters, diesters, or mixtures of monoesters and diesters may be obtained, while either the monoester or the diester may be dominant in such mixtures ("selective esterification," see above). Where the text of the present invention refers to “esterified isosorbide,” under the conditions of the method for producing and / or isolating isoidides according to the present invention, the monoester of isosorbide (specifically, monoacylated or monoacetylated isosorbide) is usually dominant. Where the text of the present invention refers to "esterified isomannides," diesters of isomannides (specifically, bisacylated or bisacetylated isomannides) are generally preferred under the conditions of the methods for producing and / or isolating isoidides according to the present invention. In certain cases, particularly when the reaction time is short and / or only a relatively small amount of acylating agent is available, monoesters of isomannides may be preferred over other forms of isomannides.

[0020] As defined above in step M4), a mixture comprising a non-esterified isoidide, as well as one or both compounds selected from the group consisting of esterified isosorbide and esterified isomannide, may also contain esterified isoidides to some extent, as described and identified in more detail below.

[0021] In certain embodiments, the present invention also provides a method for producing and / or isolating 1,4:3,6-dianhydro-L-iditol, comprising the following steps: M3a) Formula II comprising one or both compounds selected from the group consisting of 1,4:3,6-dianhydro-L-iditol and 1,4:3,6-dianhydro-D-sorbitol and 1,4:3,6-dianhydro-D-mannitol

[0022] [ka] The steps of preparing or making a mixture of the compounds, Step M3a) is the step of subjecting the mixture of compounds of formula II from step M3a) to selective esterification conditions so that a mixture is obtained containing one or both compounds selected from the group consisting of unesterified 1,4:3,6-dianhydro-L-iditol and esterified 1,4:3,6-dianhydro-D-sorbitol and esterified 1,4:3,6-dianhydro-D-mannitol. This relates to methods that include [specific methods].

[0023] In the context of steps M3) and M4) of a method for producing and / or isolating an isoidide according to the present invention as defined herein, all aspects of the present invention discussed herein apply, with necessary modifications, to steps M3a) and M4a) of a method for producing and / or isolating an isoidide according to the present invention as defined above herein.

[0024] A method for producing and / or isolating an isoidide according to the present invention as defined herein (or a method for producing and / or isolating an isoidide according to the present invention as preferred above or below), wherein the selective esterification in step M4) (or step M4a) is - This is carried out by selectively esterifying isosorbide and / or isomannide in the presence of isoizide. and / or - In the presence of a metal catalyst, preferably a metal salt catalyst Preferably, the metal is selected from the group consisting of calcium, strontium, barium, zinc, cadmium, mercury, indium, thallium, lanthanides, tin, lead, antimony, bismuth, iron, cobalt, and nickel. More preferably, the metal is selected from the group consisting of barium, mercury, lead, and bismuth. A more more preferred metal catalyst is at least one member of the group consisting of lead catalysts, preferably lead salt catalysts, more preferably lead(II) carboxylates and lead(II) oxides, or comprising the same; and even more preferably, the metal catalyst is lead(II) acetate or comprising the same. It will be implemented in And / or (preferably "and") - A compound mixture of formula II, selected from the following group of reagents: - A sulfonic acid, preferably a sulfonic acid containing a total number of carbon atoms in the range of 1 to 8, preferably the present carbon atoms forming a branched carbon chain (where structurally possible), and more preferably the sulfonic acid is selected from the group consisting of p-toluenesulfonic acid, methanesulfonic acid, and trifluoromethanesulfonic acid. - Sulfonic acid ester, preferably a sulfonic acid ester, wherein the sulfonic acid (i.e., the sulfonic acid portion of the sulfonic acid ester of the general formula R-SO2-O- (wherein R is a carbon atom and represents the sulfonic acid portion of the sulfonic acid ester)) contains a total number of carbon atoms in the range of 1 to 8, preferably the present carbon atoms (where structurally possible) form a branched carbon chain, and more preferably the sulfonic acid ester is selected from the group consisting of esters of p-toluenesulfonic acid, esters of methanesulfonic acid, and esters of trifluoromethanesulfonic acid. - Selected from the group of sulfonic acid halides, preferably sulfonate salts and sulfonic acid bromides, and more preferably sulfonate salts. Preferably, the sulfonic acid halide (i.e., the sulfonic acid portion of the sulfonic acid halide of the general formula R-SO2-X (wherein X represents a halogen atom and R represents the sulfonic acid portion of the sulfonic acid halide, including a carbon atom)) contains a total number of carbon atoms in the range of 1 to 8, preferably the present carbon atoms (where structurally possible) form a branched carbon chain, and more preferably, the sulfonic acid halide is selected from the group consisting of halides of p-toluenesulfonic acid (preferably p-toluenesulfonate), halides of methanesulfonic acid (preferably methanesulfonate), and halides of trifluoromethanesulfonic acid (preferably trifluoromethanesulfonate). - Sulfonic anhydrides, preferably sulfonic acids (plural) that form sulfonic anhydrides (i.e., general formula R a -SO2- or R b -SO2- (In the formulas, R a and R b (where is the sulfonic acid portion of the sulfonic anhydride, which contains carbon atoms) is the sulfonic acid portion of the sulfonic anhydride, which in any case contains a total number of carbon atoms in the range of 1 to 8, preferably the present carbon atoms (where structurally possible) form a branched carbon chain, and more preferably the sulfonic acid(s) that form the sulfonic anhydride is selected from the group consisting of p-toluenesulfonic acid, methanesulfonic acid, and trifluoromethanesulfonic acid. - A carboxylic acid, preferably a carboxylic acid containing a total number of carbon atoms in the range of 2 to 8, wherein the present carbon atoms (where structurally possible) form a branched carbon chain. Preferably, an aliphatic carboxylic acid containing a total number of carbon atoms in the range of 2 to 8, preferably 2 to 6, and in any case preferably the present carbon atoms (where structurally possible) form a branched carbon chain; an aliphatic carboxylic acid containing a total number of carbon atoms in the range of 2 to 8, preferably 2 to 6, which is substituted 1 to 3 times with fluorine, chlorine, bromine and / or iodine; an alicyclic carboxylic acid containing a total number of carbon atoms in the range of 4 to 8; an alicyclic carboxylic acid containing a total number of carbon atoms in the range of 4 to 8, which is substituted 1 to 3 times with fluorine, chlorine, bromine and / or iodine; benzoic acid; benzoic acid substituted once with fluorine, chlorine, bromine or iodine; nicotinic acid and nicotinic acid substituted once with fluorine, chlorine, bromine or iodine, selected from the group. - The carboxylic acid ester, preferably the carboxylic acid portion of a carboxylic acid ester of the general formula RC(O)O- (wherein R represents a carboxylic acid portion containing a carbon atom), is selected from the group consisting of carboxylic acids containing a total number of carbon atoms in the range of 2 to 8, preferably 2 to 6, and preferably the present carbon atoms form a branched carbon chain (where structurally possible). More preferably, in any case, the carboxylic acid is an aliphatic carboxylic acid containing a total number of carbon atoms in the range of 2 to 8, preferably 2 to 6, and in any case preferably the present carbon atoms (where structurally possible) form a branched carbon chain; an aliphatic carboxylic acid containing a total number of carbon atoms in the range of 2 to 8, preferably 2 to 6, which is substituted 1 to 3 times with fluorine, chlorine, bromine and / or iodine; an alicyclic carboxylic acid containing a total number of carbon atoms in the range of 4 to 8; an alicyclic carboxylic acid containing a total number of carbon atoms in the range of 4 to 8, which is substituted 1 to 3 times with fluorine, chlorine, bromine and / or iodine; benzoic acid; benzoic acid substituted once with fluorine, chlorine, bromine or iodine; and selected from the group consisting of nicotinic acid and nicotinic acid substituted once with fluorine, chlorine, bromine or iodine. - Selected from the group consisting of carboxylic acid halides, preferably carboxylic acid chlorides and carboxylic acid bromides, and more preferably carboxylic acid chlorides. Preferably, the carboxylic acid (i.e., the carboxylic acid portion of a carboxylic acid halide of the general formula RC(O)-X (wherein X represents a halogen atom and R represents the carboxylic acid portion of a carboxylic acid halide containing a carbon atom)) is selected from the group consisting of carboxylic acids containing a total number of carbon atoms in the range of 2 to 8, preferably 2 to 6, and preferably the present carbon atoms (where structurally possible) form a branched carbon chain. More preferably, in any case, the carboxylic acid is selected from the group consisting of: an aliphatic carboxylic acid containing a total number of carbon atoms in the range of 2 to 8, preferably 2 to 6, and in any case preferably the present carbon atoms (where structurally possible) form a branched carbon chain; an aliphatic carboxylic acid containing a total number of carbon atoms in the range of 2 to 8, preferably 2 to 6, which is substituted 1 to 3 times with fluorine, chlorine, bromine and / or iodine; an alicyclic carboxylic acid containing a total number of carbon atoms in the range of 4 to 8; an alicyclic carboxylic acid containing a total number of carbon atoms in the range of 4 to 8, which is substituted 1 to 3 times with fluorine, chlorine, bromine and / or iodine; benzoic acid; benzoic acid substituted once with fluorine, chlorine, bromine or iodine; nicotinic acid and nicotinic acid substituted once with fluorine, chlorine, bromine or iodine. - Carboxylic acid anhydrides, preferably carboxylic acids (plural) that form carboxylic acid anhydrides (i.e., general formula R c -C(O)- or R d -C(O)-(In each formula, R c and R d (where represents the carboxylic acid portion of a carboxylic acid anhydride containing carbon atoms) is selected from the group consisting of carboxylic acids containing a total number of carbon atoms in the range of 2 to 8, preferably 2 to 6, and preferably in all cases the present carbon atoms (where structurally possible) form a branched carbon chain. More preferably, in each case, the carboxylic acid forming the carboxylic anhydride contains a total number of carbon atoms in the range of 2 to 8, preferably 2 to 6, and in each case, preferably, the carbon atoms present form an aliphatic carboxylic acid having a branched carbon chain (where structurally possible); an aliphatic carboxylic acid containing a total number of carbon atoms in the range of 2 to 8, preferably 2 to 6, and substituted 1 to 3 times with fluorine, chlorine, bromine and / or iodine; an alicyclic carboxylic acid containing a total number of carbon atoms in the range of 4 to 8; an alicyclic carboxylic acid containing a total number of carbon atoms in the range of 4 to 8 and substituted 1 to 3 times with fluorine, chlorine, bromine and / or iodine; benzoic acid; benzoic acid substituted once with fluorine, chlorine, bromine or iodine; nicotinic acid and nicotinic acid substituted once with fluorine, chlorine, bromine or iodine, and is selected from the group consisting of Even more preferably, the carboxylic anhydride is selected from the group consisting of acetic anhydride, propionic anhydride, butyric anhydride, isobutyric anhydride (i.e., 2-methylpropanoic anhydride), pivalic anhydride (i.e., 2,2-dimethylpropanoic anhydride), valeric anhydride (i.e., pentanoic anhydride) and mixtures thereof, Even still more preferably, the carboxylic anhydride is selected from the group consisting of acetic anhydride, propionic anhydride, butyric anhydride, isobutyric anhydride (i.e., 2-methylpropanoic anhydride), pivalic anhydride (i.e., 2,2-dimethylpropanoic anhydride) and mixtures thereof, and - alkyl esters of chloroformic acid (also known as chloroformic esters), preferably, the alkyl ester group is unbranched or (where structurally possible) branched and contains a total number of carbon atoms in the range of 2 to 6, Preferably, - sulfonic anhydrides, preferably the sulfonic acid(s) forming the sulfonic anhydride (i.e., the general formula R a -SO2- or R b -SO2- (each, in the formula, R a and R b(where is the sulfonic acid portion of the sulfonic anhydride, which contains carbon atoms) in all cases contains a total number of carbon atoms in the range of 1 to 8, and more preferably the sulfonic acid(s) that form the sulfonic anhydride is selected from the group consisting of p-toluenesulfonic acid, methanesulfonic acid, and trifluoromethanesulfonic acid. and - Carboxylic acid anhydrides, preferably carboxylic acids (plural) that form carboxylic acid anhydrides (i.e., general formula R c -C(O)- or R d -C(O)-(In each formula, R c and R d (is the carboxylic acid portion of a carboxylic acid anhydride, which has the meaning defined above), but in any case is selected from the group consisting of carboxylic acids containing a total number of carbon atoms in the range of 2 to 8, preferably 2 to 6, and preferably in any case the present carbon atoms (where structurally possible) form a branched carbon chain. More preferably, in any case, the carboxylic acid forming the carboxylic acid anhydride is selected from the group consisting of: an aliphatic carboxylic acid containing a total number of carbon atoms in the range of 2 to 8, preferably 2 to 6, and in any case preferably the present carbon atoms (where structurally possible) form a branched carbon chain; an aliphatic carboxylic acid containing a total number of carbon atoms in the range of 2 to 8, preferably 2 to 6, which is substituted 1 to 3 times with fluorine, chlorine, bromine and / or iodine; an alicyclic carboxylic acid containing a total number of carbon atoms in the range of 4 to 8; an alicyclic carboxylic acid containing a total number of carbon atoms in the range of 4 to 8, which is substituted 1 to 3 times with fluorine, chlorine, bromine and / or iodine; benzoic acid; benzoic acid substituted once with fluorine, chlorine, bromine or iodine; nicotinic acid and nicotinic acid substituted once with fluorine, chlorine, bromine or iodine; More preferably, the carboxylic acid anhydride is selected from the group consisting of acetic anhydride, propionic anhydride, butyric anhydride, isobutyric anhydride, pivalic anhydride, valeric anhydride, and mixtures thereof. More preferably, the carboxylic acid anhydride is selected from the group consisting of acetic anhydride, propionic anhydride, butyric anhydride, isobutyric anhydride, pivalic anhydride, and mixtures thereof. A reagent selected from the group consisting of, More preferably, acetic anhydride or a reagent containing it. This includes a step that causes a reaction, and / or - The operation is carried out at temperatures in the range of -20°C to 50°C, preferably 10°C to 50°C, more preferably 15°C to 45°C, and even more preferably 15°C to 35°C. and / or - The reaction is carried out with a reaction time ranging from 15 minutes to 24 hours, preferably 30 minutes to 10 hours, more preferably 1 hour to 5 hours, and more preferably 1 hour to 3 hours. The method is preferable.

[0025] A method for producing and / or isolating isoidides according to the present invention, as defined herein, is preferred (or a method for producing and / or isolating isoidides according to the present invention, as described above or below as preferred), wherein the selective esterification in step M4) (or step M4a) comprises reacting a mixture of compounds of formula II with a reagent selected from the group consisting of a carboxylic acid anhydride or a subgroup of preferred reagents (as defined more in detail above herein).

[0026] In a method for producing and / or isolating an isoidide according to the present invention, as defined above herein, the selective esterification in step M4) is carried out in the presence of a metal catalyst, the metal catalyst being present in a homogeneous or heterogeneous phase, preferably in a homogeneous phase. Preferably, the total amount of the metal catalyst present in step M4) is in the range of 0.01 to 10.0 mol%, more preferably 0.05 to 5.0 mol%, and more preferably 0.1 to 3.0 mol%, relative to the molar amount of the mixture of compounds of formula II present in step M4).

[0027] In a method for producing and / or isolating isoidides according to the present invention, as defined above herein, the reagent for reacting with a mixture of compounds of formula II is or comprises a sulfonic anhydride or a carboxylic acid anhydride, the anhydride in which the anhydride may be symmetric (i.e., composed of two acidic moieties derived from the same acid) or asymmetric (i.e., composed of two acidic moieties derived from different acids). For the purposes of the present invention, symmetric sulfonic anhydrides and symmetric carboxylic acid anhydrides are preferred as reagents for reacting with a mixture of compounds of formula II.

[0028] In a method for producing and / or isolating isoidides according to the present invention, as defined above herein, the reagent for reacting with a mixture of compounds of formula II is or comprises a sulfonic acid ester or a carboxylic acid ester, wherein the ester portion of the sulfonic acid ester or the carboxylic acid ester is preferably or comprises an unbranched or (where structurally possible) branched alkyl ester containing 1 to 6, preferably 2 to 4, carbon atoms.

[0029] In a method for producing and / or isolating isoidides according to the present invention as defined above herein, the reagents for reacting with a mixture of compounds of formula II are or include carboxylic acids, carboxylic acid esters, carboxylic acid halides and / or carboxylic acid anhydrides, wherein the carboxylic acid represents a carboxylic acid (as described above) that forms the carboxylic acid or the carboxylic acid ester, the carboxylic acid halide and / or the carboxylic acid anhydride, preferably acetic acid; acetic acid substituted 1 to 3 times with fluorine, chlorine, bromine and / or iodine; propionic acid; fluorine, chlorine Selected from the group consisting of propionic acid substituted 1 to 3 times with bromine and / or iodine; butyric acid; butyric acid substituted 1 to 3 times with fluorine, chlorine, bromine and / or iodine; pivalic acid; pivalic acid substituted 1 to 3 times with fluorine, chlorine, bromine and / or iodine; valeric acid; valeric acid substituted 1 to 3 times with fluorine, chlorine, bromine and / or iodine; caproic acid; caproic acid substituted 1 to 3 times with fluorine, chlorine, bromine and / or iodine; benzoic acid, benzoic acid substituted once with fluorine, chlorine, bromine or iodine; nicotinic acid and nicotinic acid substituted once with fluorine, chlorine, bromine or iodine.

[0030] In a method for producing and / or isolating an isoidide according to the present invention as defined above herein, the total molar amount of reagent to react with the mixture of compounds of formula II present in step M4) is preferably in the range of 0.5 to 2 moles, more preferably 0.5 to 1.5 moles, of the molar amount of the mixture of compounds of formula II present in step M4).

[0031] Generally, mixtures of compounds of formula II can be reacted with reagents as defined above (or reagents defined as preferred above) in step M4) (or M4a) of the method for producing and / or isolating isoidides according to the present invention, by reacting the compounds of formula II (or mixtures thereof, respectively) with the reagents of the selected particular reagent according to methods known in the art for esterification of that particular reagent. As described above, the stereoselective process of the esterification reaction is, in principle, independent of the reaction mechanism, but is mainly controlled by the stereochemistry of the (different) compounds of formula II and may be influenced to some extent by the properties of the selected reagent and / or the properties of the selected catalyst. Nevertheless, adjusting certain parameters of the reaction in step M4) (or M4a)) can favorably influence the outcome of selective esterification, for example, in terms of the amount (or ratio) of the desired reaction product obtained.

[0032] The temperature range and reaction time range defined herein for the method of producing and / or isolating an isoidide according to the present invention (step M4) or M4a) above characterize preferred parameters that yield a mixture (usually including esterified isoidides) containing a non-esterified isoidide and one or both compounds selected from the group consisting of esterified isosorbide and esterified isomannide, including a high content of non-esterified isoidides and a high content of other esterified dianhydrohexitol isomers.

[0033] The temperature range and reaction time range (for step M4 or M4a) as defined above herein are particularly suitable for the method of producing and / or isolating isoidides according to the present invention, and the reagents for reacting a mixture of compounds of formula II are carboxylic acid anhydrides or sulfonic acid anhydrides, preferably carboxylic acid anhydrides, more preferably carboxylic acids (plural) that form carboxylic acid anhydrides (i.e., each of the general formula R a -C(O)- or R bThe carboxylic acid portion of the -C(O)- carboxylic acid anhydride is selected from the group consisting of carboxylic acids containing a total of 2 to 8, preferably 2 to 6, carbon atoms, in any case, or contains such anhydride.

[0034] Similarly, the temperature range and reaction time range (for step M4 or M4a) as defined above herein are particularly suitable for a method of producing and / or isolating isoidides according to the present invention, the reaction being carried out in the presence of a metal catalyst, preferably a preferred or more preferred metal catalyst as defined above herein.

[0035] In certain variations of the method for producing and / or isolating isoidides according to the present invention, as defined above herein, step M4) is carried out in the presence of one or more organic solvents that are inert (or catalytically active only) under reaction conditions, or step M4) is carried out in the absence of such organic solvents. Suitable inert (or catalytically active only) organic solvents are selected from ether solvents, ester solvents, nitrile solvents, ketone solvents, amide solvents, aromatic solvents, aliphatic solvents, haloaromatic solvents, haloaliphatic solvents and mixtures thereof, as are generally known in the art. Solvents that are catalytically active only in the reaction are not consumed in the reaction, as is generally known in the art.

[0036] In preferred variations of the method for producing and / or isolating isoidides according to the present invention, the reagent for reacting with a mixture of compounds of formula II is used as (or functions as) the solvent in step M4). In these preferred variations, preferably, no additional organic solvents that are inert (or only catalytically active as specified above) under the reaction conditions are present in step M4).

[0037] Methods for producing and / or isolating isoidides according to the present invention, as defined herein (or methods for producing and / or isolating isoidides according to the present invention, as described above or below as preferred), and the mixture of compounds of formula II prepared or made in step M3) includes or comprises isoidides, isosorbides and isomannides, Preferably, - The isoidide is present in a total amount of 10 to 95 mol%, preferably 40 to 95 mol%, and more preferably 50 to 90 mol%, relative to the total molar amount of the mixture of compounds of formula II. or - The isoidide is present in a total amount of 40 to 70 mol%, preferably 45 to 65 mol%, and more preferably 50 to 60 mol%, relative to the total molar amount of the mixture of compounds of formula II.

[0038] In a method for producing and / or isolating an isoidide according to the present invention as defined above herein, the mixture of compounds of formula II prepared or provided in step M3) includes or comprises isoidide, isosorbide, and isomannide, which are preferably prepared by isomerization and epimerization, respectively, from one or more compounds selected from the group consisting of isosorbide, isomannide, and mixtures thereof, more preferably isosorbide, particularly under mobile hydrogenation conditions (see step M2) in particular, which are described and specified in more detail below).

[0039] Under the conditions of the method for producing and / or isolating isoidides according to the present invention as defined herein, preferably under the conditions of step M2), isoidides are typically found to be present in mixtures containing or comprising isoidides, isosorbide, and isomannide in a total amount (or a preferred amount as defined above) in the range of 40–70 mol% relative to the total molar amount of the mixture of compounds of formula II. Therefore, the aforementioned total amount of isoidides in the range of 40–70 mol% is considered to represent the thermodynamic equilibrium amount of isoidides produced under the conditions of the method for producing and / or isolating isoidides according to the present invention as defined herein, specifically under the conditions of step M2).

[0040] However, a mixture comprising or containing isoidides, isosorbide, and isomannide, obtained under the conditions of a method for producing and / or isolating isoidides according to the present invention as defined herein, can be further enriched with isoidides by, for example, physicochemical methods commonly known in the art, including, for example, distillation, crystallization, and chromatography. As a result of these steps of enriching the mixture comprising or containing isoidides, isosorbide, and isomannide with isoidides, isoidides may be present in such enriched mixture in a total amount of up to 95 mol%, as defined above.

[0041] A method for producing and / or isolating an isoidide according to the present invention, as defined herein (or a method for producing and / or isolating an isoidide according to the present invention, as described above or below as preferred), is more preferable. - In a mixture obtained in step M4) containing a non-esterified isoidide and one or both compounds selected from the group consisting of esterified isosorbide and esterified isomannide, - The molar ratio of non-esterified isoidide to esterified isoidide is in the range of 75:25 to 98:2, preferably 80:20 to 95:5. and / or - The molar ratio of present non-esterified isosorbide to present esterified isosorbide is in the range of 20:80 to 0.01:99.99, preferably 5:95 to 0.5:99.5. and / or - The molar ratio of the present non-esterified isomannide to the present esterified isomannide is in the range of 20:80 to 0.01:99.99, preferably 5:95 to 0.1:99.9. and / or - The mixture obtained in step M4) containing a non-esterified isoidide and one or both compounds selected from the group consisting of esterified isosorbide and esterified isomannide comprises isoidide, isomannide-2,5-diacetate and isosorbide monoacetate, preferably isosorbide-5-monoacetate.

[0042] In independent experiments, it has been found that, depending on the allowable reaction time, the molar ratio of present esterified (especially acetylated) isosorbide to present non-esterified isosorbide in a mixture containing the non-esterified isoidide and esterified (especially monoacylated, especially monoacetylated) isosorbide and optionally esterified (especially bisacylated, especially bisacetylated) isomannide can be 99:1 or greater. Obtaining such a high molar excess of esterified isosorbide from the method for producing and / or isolating isoidides of the present invention is particularly beneficial because it greatly simplifies the separation of isosorbide (each esterified isosorbide) from the mixture obtained in step M4).

[0043] In further embodiments, methods for producing and / or isolating isoidides according to the present invention, as defined herein (or methods for producing and / or isolating isoidides according to the present invention, as described above or below as preferred), are also preferred. - In a mixture containing the non-esterified isoidide obtained in step M4) and one or both compounds selected from the group consisting of esterified isosorbide and esterified isomannide, - The molar ratio of non-esterified isoidide to esterified isoidide is 80:20 or higher. and - The molar ratio of existing non-esterified isosorbide to existing esterified isosorbide is 5:95 or less. and - The molar ratio of existing non-esterified isomannides to existing esterified isomannides is 5:95 or less.

[0044] Furthermore, a method for producing and / or isolating isoidides in accordance with the present invention as defined herein (or a method for producing and / or isolating isoidides in accordance with the present invention as preferred above or below) is preferred, and the method includes the following additional steps (preferably performed before step M3 as defined above): M2) One or more compounds selected from the group consisting of isosorbide, isomannide, isosorbide esters, isomannide esters, and mixtures thereof. Preferably, one or more compounds selected from the group consisting of isosorbide, isomannide, and mixtures thereof, more preferably isosorbide. Preferably, one or more compounds selected from the group consisting of isosorbide, isomannide, and mixtures thereof, preferably isosorbide, (may be multiple) are used as an organic (preferably cycloheteroaliphatic) hydroxyl compound mixture, containing a total amount of isosorbide in the range of 90 to 99.5% by mass, preferably 95 to 99.5% by mass, relative to the total mass of sorbitol, mannitol, isosorbide, isomannide, and sorbitan derivatives (sorbitan derivatives are selected from the group consisting of 1,4-sorbitan, 3,6-sorbitan, 2,5-mannitan, 2,6-sorbitan, 1,5-sorbitan, 2,5-iditan, and mixtures thereof) present in the mixture of organic (preferably cycloheteroaliphatic) hydroxyl compounds. Under conditions of mobile hydrogenation in the presence of a transition metal catalyst and preferably in the presence of hydrogen, Preferably, the transition metal is selected from the group consisting of nickel, copper, ruthenium, and rhodium, and more preferably, the transition metal is ruthenium or nickel. Preferably - Preferably in the presence of a polar solvent selected from the group consisting of alcohols, preferably alcohols containing 1 to 6 carbon atoms, water, and mixtures thereof, More preferably, in the presence of a solvent containing or comprising one or more alcohols, each containing 1 to 6, preferably 2 to 4, carbon atoms, and even more preferably in the presence of 2-propanol, and / or - At a total pressure in the range of 200 to 10000 kPa, preferably 1000 to 7500 kPa, more preferably 2000 to 5000 kPa, and / or - At temperatures ranging from 100°C to 250°C, preferably from 150°C to 235°C, The reaction yields a mixture of compounds of formula II as defined above.

[0045] In a method for producing and / or isolating isoidides according to the present invention as defined above, step M2) is carried out in an organic solvent as defined above, preferably a polar solvent, i.e., a non-aqueous solvent, and this preferred alternative method for producing and / or isolating isoidides according to the present invention has the beneficial effect that, since the reagents preferably used in step M4) for reacting with a mixture of compounds of formula II are normally water-sensitive, the product produced from step M2) (i.e., a mixture of compounds of formula II as defined above) can be easily used in steps M3) and / or M4) without the time-consuming water removal work that might otherwise be necessary.

[0046] In a method for producing and / or isolating isoidides according to the present invention, as defined above herein, step M2) is carried out in the presence of a transition metal catalyst, the transition metal catalyst being present in a homogeneous or heterogeneous phase, preferably in a heterogeneous phase. Preferred transition metal catalysts present in the heterogeneous phase in step M2) are (i) supported heterogeneous transition metal catalysts, preferably ruthenium on carbon, and (ii) heterogeneous skeletal transition metal catalysts, preferably heterogeneous skeletal nickel catalysts, more preferably heterogeneous skeletal nickel catalysts prepared from nickel alloys, e.g., those described in US 1,628,190, and those commonly known in the art as "Raney nickel," and even more preferably molybdenum-promoted, and even more preferably molybdenum-promoted Raney nickel catalysts, which are heterogeneous skeletal nickel catalysts (as previously defined herein or previously defined as preferred herein).

[0047] Preferably, in a method for producing and / or isolating an isoidide according to the present invention, as defined above herein, the transition metal catalyst present in the heterogeneous phase of step M2) is present in a solid form selected from the group consisting of powder, slurry and formed object (the formed object preferably includes extruded objects and tablets).

[0048] In a preferred variation of the method for producing and / or isolating an isoidide according to the present invention, as defined herein (or a preferred method for producing and / or isolating an isoidide according to the present invention as described above or below), the method includes the following additional steps: M1) A step of reacting one or both compounds selected from the group consisting of sorbitol (preferably D-sorbitol), mannitol (preferably D-mannitol), and mixtures thereof, under acidic conditions to obtain (at least) one or more compounds selected from the group consisting of isosorbide, isomannide, and mixtures thereof. Preferably, the step of obtaining one or more compounds selected from the group consisting of isosorbide, isomannide, and mixtures thereof for use in (or for) step M2).

[0049] The reaction defined in step M1) is generally known in the art as an acid-catalyzed bimolecular dehydration reaction that proceeds via the respective intermediate compounds sorbitan, mannitane, or iditane (for example, at least aspects thereof are known from reference US2009 / 0259057).

[0050] In one preferred particular variant of the method for producing and / or isolating isoidides according to the present invention as defined herein (or the method for producing and / or isolating isoidides according to the present invention as preferred above or below), one or more compounds selected from the group consisting of isosorbide, isomannide and mixtures thereof (as defined herein above) used in (or for) step M2) preferably, are used as a mixture of organic (preferably cycloheteraliphatic) hydroxyl compounds containing a total amount of isosorbide in the range of 90 to 99.5% by mass, preferably 95 to 99.5% by mass, based on the total mass of sorbitol, mannitol, isosorbide, isomannide and sorbitan derivatives (selected from the group consisting of 1,4-sorbitan, 3,6-sorbitan, 2,5-mannitan, 2,6-sorbitan, 1,5-sorbitan, 2,5-iditan and mixtures thereof (as specified below)) in the mixture of organic (preferably cycloheteraliphatic) hydroxyl compounds. In this preferred particular variant of the method for producing and / or isolating isoidides, the mixture of organic (preferably cycloheteraliphatic) hydroxyl compounds (in addition to isosorbide as previously defined herein) preferably further comprises 0.5% by mass or more, preferably in the range of 0.5 to 5% by mass, of the total mass of sorbitol, mannitol, isosorbide, isomannide, and sorbitan derivatives present in the mixture of organic (preferably cycloheteraliphatic) hydroxyl compounds (as defined above). The mixture or mixture of organic (preferably cycloheteraliphatic) hydroxyl compounds is known by itself in the art, for example, as described in C. Dussenne et al., Green Chemistry (2017) 19, 5332-5344 (e.g., "crude isosorbide"). The sorbitan derivatives described above, selected from the group consisting of 1,4-sorbitan, 3,6-sorbitan, 2,5-mannitane, 2,6-sorbitan, 1,5-sorbitan, 2,5-iditane, and mixtures thereof, have the following chemical structure:

[0051] [ka] It has (as is well known in the art).

[0052] Furthermore, a method for producing and / or isolating isoidides according to the present invention, as defined herein (or a method for producing and / or isolating isoidides according to the present invention, as described above or below as preferred), the method further comprising the following additional steps: M5) The non-esterified isoidide is separated from the mixture obtained in step M4) which contains the non-esterified isoidide and one or both compounds selected from the group consisting of esterified isosorbide and esterified isomannide, preferably by phase separation, and more preferably by liquid-liquid extraction. A step of obtaining and / or isolating a non-esterified isoidide.

[0053] In a method for producing and / or isolating isoidides according to the present invention as defined above herein (step M5), the non-esterified isoidide can be separated, preferably by phase separation or chromatography, from a mixture obtained in step M4) comprising the non-esterified isoidide and one or both compounds selected from the group consisting of esterified isosorbide and esterified isomannide (and optionally also with the esterified isoidide). Phase separation is a preferred method for separating the non-esterified isoidide in step M5) of the method for producing and / or isolating isoidides according to the present invention.

[0054] In a method for producing and / or isolating an isoidide according to the present invention as defined above herein (step M5), the non-esterified isoidide is separated by phase separation from a mixture obtained in step M4) comprising the non-esterified isoidide and one or both compounds selected from the group consisting of esterified isosorbide and esterified isomannide (and optionally with the esterified isoidide), wherein the phase separation preferably includes liquid-liquid extraction, crystallization and distillation. Liquid-liquid extraction is a preferred method for the phase separation in step M5) of the method of the present invention.

[0055] In step M5), the aqueous liquid-liquid extraction (step M4) of non-esterified isoidides obtained using an organic, water-immiscible organic solvent (step M4) (preferably ethyl acetate or containing ethyl acetate), which includes or may contain or may be a mixture containing at least a majority of one or both compounds selected from the group consisting of esterified isosorbide and esterified isomannide, and optionally also containing esterified isoidides), has been found in independent experiments to be a particularly gentle, simple, and efficient method for separating non-esterified isoidides (by phase separation) in high yield from a mixture containing non-esterified isoidides and one or both compounds selected from the group consisting of esterified isosorbide and esterified isomannide, and optionally also containing esterified isoidides.

[0056] Therefore, a method for producing and / or isolating an isoidide according to the present invention, as defined herein (or a method for producing and / or isolating an isoidide according to the present invention, as described above or below as preferred), is preferred, and the method is at least the following steps (i.e., a method for producing and / or isolating an isoidide according to the present invention may further include additional steps, e.g., one or more or all of steps M1), M2), M6), and / or M7) disclosed herein, preferably in a sequential order of these numberings): M3) A compound comprising one or both selected from the group consisting of isoizides, isosorbides, and isomannides (as described and specified in more detail above), Formula II

[0057] [ka] A step of preparing or making a mixture of the compounds, Step M4) Subjecting a mixture of compounds of formula II from step M3) to conditions for selective esterification so that a mixture (or each of them) is obtained, comprising one or both compounds selected from the group consisting of a non-esterified isoidide and esterified isosorbide and esterified isomannide, and M5) The non-esterified isoidide is separated from the mixture obtained in step M4) which contains one or both compounds selected from the group consisting of esterified isosorbide and esterified isomannide, preferably by phase separation, more preferably by liquid-liquid extraction (as described and specified in more detail above), Steps to obtain and / or isolate non-esterified isoidides. Includes.

[0058] Methods for producing and / or isolating isoidides according to the present invention, as defined herein (or methods for producing and / or isolating isoidides according to the present invention, as described above or below as preferred), which further include the following additional steps: M6) A mixture comprising one or both compounds selected from the group consisting of esterified isosorbide and esterified isomannide, preferably an esterified isoidide obtained after separation in step M5), and / or further comprising one or more of these reaction products, preferably a mixture in which one or more reaction products comprise one or more compounds selected from the group consisting of isosorbide, isomannide, and mixtures thereof, preferably further comprising an isoidide. Preferably, one or more steps include providing or preparing a mixture of the compound of formula II for step M3) (or for step M3), And / or (preferably "or") M7) is a step of hydrolyzing a mixture comprising one or both compounds selected from the group consisting of esterified isosorbide and esterified isomannide, preferably further comprising the esterified isoidide obtained after separation in step M5), Preferably, the isosorbide and / or isomannide (preferably the isoidide also obtained thus) obtained in step M2) (or for step M2) is used in step It also includes.

[0059] In steps M6) and / or M7) of the method for producing and / or isolating isoidides according to the present invention, esterified dianhydrohexitol isomers that have not been converted to the desired product isoidide can be recovered and recycled into the method or process according to the present invention to further increase the overall yield of the desired product isoidide. Therefore, the effectiveness of the method can be further advantageously increased by carrying out the method for producing and / or isolating isoidides according to the present invention, which includes steps M6) and / or M7).

[0060] The present invention also relates to a composition comprising a mixture comprising (at least) a non-esterified isoidide and one or both compounds selected from the group consisting of esterified isosorbide and esterified isomannide, as defined above, in (or for) step M4) of a method for producing and / or isolating an isoidide according to the present invention (or a method for producing and / or isolating an isoidide according to each of the present inventions as preferred herein). The composition may contain further components. For example, the composition may further include esterified isoidides, and more commonly, further include esterified isoidides. When used in the context of the present invention, the term "esterified isoidide" includes the group consisting of monoesters of isoidides, diesters of isoidides, and mixtures of monoesters of isoidides and diesters of isoidides, as described above.

[0061] In general, in the context of methods for producing and / or isolating isoidides according to the present invention, all aspects of the present invention discussed herein are applied with necessary modifications to compositions comprising a mixture of a non-esterified isoidide according to the present invention and one or both compounds selected from the group consisting of esterified isosorbide and esterified isomannide, as defined above and below herein. And vice versa, in the context of compositions comprising a mixture of a non-esterified isoidide according to the present invention and one or both compounds selected from the group consisting of esterified isosorbide and esterified isomannide, all aspects of the present invention discussed herein are applied with necessary modifications to methods for producing and / or isolating isoidides according to the present invention, as defined herein.

[0062] A composition according to the present invention as defined above (or a composition according to the present invention as described above or below as preferred) is preferred, wherein the present esterified isosorbide, present esterified isomannide, and present esterified isoidide are all esterified with a carboxylic acid containing a total number of carbon atoms in the range of 2 to 8. Preferably, the present esterified isosorbide, present esterified isomannide, and present esterified isoidide are all esterified with the same carboxylic acid containing a total number of carbon atoms in the range of 2 to 8. For example, in such preferred compositions according to the present invention, the present esterified isosorbide, present esterified isomannide, and present esterified isoidide are all esterified with acetic acid (i.e., all of the esterified compounds present in the composition exist as acetic acid esters).

[0063] A composition according to the present invention as defined above (or a composition according to the present invention as described above or below as preferred) is even more preferred. - Esterified isosorbide is esterified by reacting isosorbide with a reagent selected from the group consisting of carboxylic acid anhydrides, and the carboxylic acid(s) forming the carboxylic acid anhydride are selected in all cases from the group consisting of carboxylic acids containing a total number of carbon atoms ranging from 2 to 8. and / or - Esterified isomannides are esterified by reacting an isomannide with a reagent selected from the group consisting of carboxylic acid anhydrides, and the carboxylic acid(s) forming the carboxylic acid anhydride are selected in all cases from the group consisting of carboxylic acids containing a total number of carbon atoms ranging from 2 to 8.

[0064] Compositions according to the present invention as defined above (or compositions according to the present invention as preferred above or below) are also preferred. - The molar ratio of non-esterified isoidides present in the composition to the total of esterified isoidides, esterified isosorbides, and esterified isomannides present in the composition is in the range of 40:60 to 65:35, preferably in the range of 45:55 to 60:40. and / or - The molar ratio of non-esterified isoidide to esterified isoidide present in the composition is in the range of 75:25 to 98:2, preferably in the range of 80:20 to 95:5. and / or - The molar ratio of non-esterified isosorbide to esterified isosorbide present in the composition is in the range of 20:80 to 0.01:99.99, preferably in the range of 5:95 to 0.5:99.5. and / or - The molar ratio of non-esterified isomannides present in the composition to esterified isomannides is in the range of 20:80 to 0.01:99.99, preferably in the range of 5:95 to 0.1:99.9. and / or - The composition comprises isoidide, isomannide-2,5-diacetate, and isosorbide monoacetate, preferably isosorbide-5-monoacetate.

[0065] A composition according to the present invention as defined above (or a composition according to the present invention as described above or below as preferred) is particularly preferred. - Existing esterified isosorbides, esterified isomannides, and esterified isoidides are all esterified with a carboxylic acid containing a total number of carbon atoms ranging from 2 to 8. and - The molar ratio of non-esterified isoidide to esterified isoidide present in the composition is in the range of 75:25 to 98:2, preferably in the range of 80:20 to 95:5.

[0066] The compositions according to the present invention as defined above are valuable starting materials for a method of producing and / or isolating isoidides according to the present invention and / or valuable intermediates in a method of producing and / or isolating isoidides according to the present invention.

[0067] Compositions according to the present invention as defined above (or compositions according to the present invention as preferred above or below) are also preferred. - The molar ratio of non-esterified isoidide to present esterified isoidide in the composition is 80:20 or higher. and - The molar ratio of non-esterified isosorbide to esterified isosorbide present in the composition is 5:95 or less. and - The molar ratio of non-esterified isomannides present in the composition to esterified isomannides present is 5:95 or less.

[0068] The present invention further relates to compositions according to the present invention as defined herein (or compositions according to the present invention as described above or below as preferred), which are obtained or can be obtained by methods of producing and / or isolating isoidides according to the present invention as defined herein (or methods of producing and / or isolating isoidides according to the present invention as preferred above or below).

[0069] In general, in the context of a method for producing and / or isolating isoidides according to the present invention as defined above, and in the context of a composition comprising a mixture containing a non-esterified isoidide according to the present invention and one or both compounds selected from the group consisting of esterified isosorbide and esterified isomannide, as defined above, all aspects of the present invention discussed herein, with necessary modifications, apply to compositions according to the present invention that can be obtained by the method for producing and / or isolating isoidides according to the present invention as defined above and below. The reverse is also true; in the context of a composition according to the present invention that can be obtained by the method for producing and / or isolating isoidides according to the present invention as defined above and below, all aspects of the present invention discussed herein, with necessary modifications, apply to the method for producing and / or isolating isoidides according to the present invention as defined above, and in compositions comprising a mixture containing a non-esterified isoidide according to the present invention and one or both compounds selected from the group consisting of esterified isosorbide and esterified isomannide, as defined above.

[0070] Furthermore, the present invention provides compositions according to the present invention as defined above (or compositions according to the present invention as described above or below as preferred), - In a method for producing and / or isoidides, preferably as starting materials or intermediates, and / or - A method for separating isoidides from other dianhydrohexitols, preferably from a mixture of other dianhydrohexitols or dianhydrohexitol isomers containing isosorbide and / or isomannide, Preferably, it relates to its use as a starting material or as an intermediate.

[0071] In general, in the context of a method for producing and / or isolating isoidides according to the present invention as defined above, in the context of a composition comprising a mixture containing a non-esterified isoidide according to the present invention and one or both compounds selected from the group consisting of esterified isosorbide and esterified isomannide, and / or in the context of a composition according to the present invention that can be obtained by a method for producing and / or isolating isoidides according to the present invention as defined above, all aspects of the present invention discussed herein are applicable to the use of a composition according to the present invention as defined above, with necessary modifications. The reverse is also true; in the context of a composition according to the present invention as defined above, all aspects of the present invention discussed herein are applicable to a method for producing and / or isolating isoidides according to the present invention as defined above, in a composition comprising a mixture containing a non-esterified isoidide according to the present invention and one or both compounds selected from the group consisting of esterified isosorbide and esterified isomannide, and to a composition according to the present invention that can be obtained by a method for producing and / or isolating isoidides according to the present invention as defined above and below, with necessary modifications.

[0072] Furthermore, the present invention relates to the use of a method comprising the step of selective esterification of a mixture of dianhydrohexitol isomers containing an isoidide (preferably a mixture of compounds of formula II as defined above) for separating the isoidide from the mixture of dianhydrohexitol isomers, preferably from the mixture of compounds of formula II as defined above (or a mixture of compounds of formula II as preferred above), preferably a method for producing and / or isolating an isoidide according to the present invention (or a method for producing and / or isolating an isoidide according to the present invention as preferred above or below).

[0073] In general, in the context of a method for producing and / or isolating isoidides according to the present invention as defined above, in the context of a composition comprising a mixture of a non-esterified isoidide according to the present invention and one or both compounds selected from the group consisting of esterified isosorbide and esterified isomannide, in the context of a composition according to the present invention that can be obtained by a method for producing and / or isolating isoidides according to the present invention as defined above, and / or in the context of the use of such compositions, all aspects of the present invention discussed herein, with necessary modifications, are applicable to the use of a method comprising a selective esterification step according to the present invention as defined above. The reverse is also true, and in the context of using a method comprising a selective esterification step according to the present invention as defined above, all aspects of the present invention discussed herein, with necessary modifications, apply to methods for producing and / or isolating isoidides according to the present invention as defined above, to compositions comprising a mixture of a non-esterified isoidide according to the present invention and one or both compounds selected from the group consisting of esterified isosorbide and esterified isomannide, as defined above, to compositions according to the present invention that can be obtained by methods for producing and / or isolating isoidides according to the present invention as defined above and below, and to the use of compositions according to the present invention as defined above.

[0074] Preferably, the use of a method comprising a selective esterification step according to the present invention, as defined above (or a method comprising a selective esterification step according to the present invention, as described above as preferred), the method comprising the steps of selectively esterifying a dianhydrohexitol isomer other than isoidide, and subsequently separating the unesterified isoidide from a mixture of esterified dianhydrohexitol isomers.

[0075] As described, isoidides or modified isoidides are of particular interest as building blocks (specifically as monomers) for polymers, for example, for biodegradable polymers and / or polymers derived from renewable natural resources. Examples include polyesters produced by polycondensation of isoidides with dicarboxylic acids or anhydrides, and polycarbonates produced by reaction with bifunctional carboxyl compounds, such as phosgene. Isoidides are also useful in other polymerizations where other diols are conventionally used. For example, bisglycidyl ethers of isoidides can be used as a substitute for bisphenol-A in epoxy resins.

[0076] Accordingly, the present invention also relates to a method for producing polymers comprising isoidide monomers or modified isoidide monomers (and / or the use of isoidide monomers or modified isoidide monomers for producing polymers), the method (or use) comprising the step of producing or isolating isoidide monomers and / or modified isoidide monomers by a method for producing and / or isolating isoidides according to the present invention as defined herein (or by a method for producing and / or isolating isoidides according to the present invention as described herein as preferred), or by a method including a method for producing and / or isolating isoidides according to the present invention as defined herein (or by a method for producing and / or isolating isoidides according to the present invention as described herein as preferred).

[0077] In general, in the context of a method for producing and / or isolating isoidides according to the present invention as defined above; in the context of a composition comprising a mixture of a non-esterified isoidide according to the present invention and one or both compounds selected from the group consisting of esterified isosorbide and esterified isomannide, as defined above; in the context of a composition according to the present invention that can be obtained by a method for producing and / or isolating isoidides according to the present invention as defined above; in the context of the use of a composition as defined above; and / or in the context of the use of a method comprising a selective esterification step according to the present invention as defined above, all aspects of the present invention discussed herein, with necessary modifications, are applicable to a method for producing (or for use in) polymers as defined above. The reverse is also true, and in the context of a method (or use for production) of polymers according to the present invention as defined above, all aspects of the present invention discussed herein, with necessary modifications, apply to a method for producing and / or isolating isoidides according to the present invention as defined above, to a composition comprising a mixture of a non-esterified isoidide and one or both compounds selected from the group consisting of esterified isosorbide and esterified isomannide, as defined above, to a composition according to the present invention that can be obtained by a method for producing and / or isolating isoidides according to the present invention as defined above and below, to a use of a composition according to the present invention as defined above, and to a method comprising a selective esterification step according to the present invention as defined above.

[0078] The present invention is further summarized and described by the following embodiments A1 to A15: A1. Formula I

[0079] [ka] A method for producing and / or isoliding the isoidide of, The following steps: M3) Formula II comprising one or both compounds selected from the group consisting of isoidides, isosorbides, and isomannides.

[0080] [ka] The steps of preparing or making a mixture of the compounds, Step M4) Subjecting the mixture of compounds of formula II from step M3) to selective esterification conditions so that a mixture is obtained containing one or both compounds selected from the group consisting of a non-esterified isoidide and esterified isosorbide and esterified isomannide. Methods that include...

[0081] A2. The selective esterification in step M4) - This is carried out by selectively esterifying isosorbide and / or isomannide in the presence of isoizide. and / or - In the presence of a metal catalyst, preferably a metal salt catalyst Preferably, the metal is selected from the group consisting of calcium, strontium, barium, zinc, cadmium, mercury, indium, thallium, lanthanides, tin, lead, antimony, bismuth, iron, cobalt, and nickel. It will be implemented in and / or - A compound mixture of formula II, selected from the following group of reagents: - Sulfonic acid, preferably a sulfonic acid containing a total number of carbon atoms in the range of 1 to 8, - Sulfonic acid ester, preferably a sulfonic acid ester containing a total number of carbon atoms in the range of 1 to 8, - Selected from the group of sulfonic acid halides, preferably sulfonate salts and sulfonic acid bromides, Preferably, in either case, a sulfonic acid halide containing a total number of carbon atoms in the range of 1 to 8, - The sulfonic anhydride, preferably the sulfonic acid(s) forming the sulfonic anhydride, contains a total number of carbon atoms ranging from 1 to 8 in all cases. - Carboxylic acids, preferably carboxylic acids containing a total number of carbon atoms in the range of 2 to 8, - The carboxylic acid ester, preferably the carboxylic acid, is selected from the group consisting of carboxylic acids containing a total number of carbon atoms in the range of 2 to 8 in any case. - Selected from the group consisting of carboxylic acid halides, preferably carboxylic acid chlorides and carboxylic acid bromides, Preferably, the carboxylic acid is selected from the group consisting of carboxylic acids containing a total number of carbon atoms in the range of 2 to 8 in any case. - The carboxylic acid anhydride, preferably the carboxylic acid(s) that form the carboxylic acid anhydride, is selected in all cases from the group consisting of carboxylic acids containing a total number of carbon atoms in the range of 2 to 8. and - Alkyl esters of chloroformic acid, preferably in which the alkyl ester group is unbranched or branched and contains a total number of carbon atoms in the range of 2 to 6. This includes a step that causes a reaction, and / or - The operation is carried out at temperatures in the range of -20°C to 50°C, preferably 10°C to 50°C, more preferably 15°C to 45°C, and even more preferably 15°C to 35°C. and / or - The reaction is carried out with a reaction time ranging from 15 minutes to 24 hours, preferably 30 minutes to 10 hours, more preferably 1 hour to 5 hours, and more preferably 1 hour to 3 hours. The method described in embodiment A1.

[0082] A3. The mixture of compounds of formula II prepared or made in step M3) includes or comprises isoidide, isosorbide and isomannide, Preferably, isoidide - In a total amount in the range of 10 to 95 mol%, preferably in the range of 40 to 95 mol%, and more preferably in the range of 50 to 90 mol%, relative to the total molar amount of the mixture of compounds of formula II, or - In a total amount in the range of 40 to 70 mol%, preferably in the range of 45 to 65 mol%, and more preferably in the range of 50 to 60 mol%, relative to the total molar amount of the mixture of compounds of formula II. A method according to any of the existing or prior embodiments.

[0083] A4. - In a mixture obtained in step M4) containing a non-esterified isoidide and one or both compounds selected from the group consisting of esterified isosorbide and esterified isomannide, - The molar ratio of non-esterified isoidide to esterified isoidide is in the range of 75:25 to 98:2, preferably in the range of 80:20 to 95:5. and / or - The molar ratio of the present non-esterified isosorbide to the present esterified isosorbide is in the range of 20:80 to 0.01:99.99, preferably in the range of 5:95 to 0.5:99.5. and / or - The molar ratio of the present non-esterified isomannide to the present esterified isomannide is in the range of 20:80 to 0.01:99.99, preferably in the range of 5:95 to 0.1:99.9. and / or - The mixture obtained in step M4) contains a non-esterified isoidide and one or both compounds selected from the group consisting of esterified isosorbide and esterified isomannide, and preferably contains isoidide, isomannide-2,5-diacetate and isosorbide monoacetate, preferably isosorbide-5-monoacetate. The method according to any of the preceding embodiments.

[0084] A5. Additional steps: M2) One or more compounds selected from the group consisting of isosorbide, isomannide, isosorbide esters, isomannide esters, and mixtures thereof. Preferably, one or more compounds selected from the group consisting of isosorbide, isomannide, and mixtures thereof, more preferably isosorbide. Preferably, one or more compounds selected from the group consisting of isosorbide, isomannide, and mixtures thereof, preferably isosorbide, are used as a mixture of organic hydroxyl compounds, containing a total amount of isosorbide in the range of 90 to 99.5% by mass, preferably 95 to 99.5% by mass, relative to the total mass of sorbitol, mannitol, isosorbide, isomannide, and sorbitan derivatives (selected from the group consisting of 1,4-sorbitan, 3,6-sorbitan, 2,5-mannitan, 2,6-sorbitan, 1,5-sorbitan, 2,5-iditan, and mixtures thereof) present in the mixture of organic hydroxyl compounds. Under conditions of mobile hydrogenation in the presence of a transition metal catalyst and preferably in the presence of hydrogen, Preferably in the presence of a polar solvent selected from the group consisting of alcohols, water, and mixtures thereof, The step of reacting to obtain a compound mixture of formula II as described in either embodiment A1 or A3. A method according to any of the preceding embodiments, preferably the method according to embodiment A3, including the method described above.

[0085] A6. Additional steps: M1) One or more compounds selected from the group consisting of isosorbide, isomannide, and mixtures thereof are obtained by reacting one or both compounds selected from the group consisting of sorbitol, mannitol, and mixtures thereof under acidic conditions. Preferably, this step yields one or more compounds selected from the group consisting of isosorbide, isomannide, and mixtures thereof, which will be used in step M2). The method according to embodiment A5, which includes the following:

[0086] A7. Additional steps: M5) The non-esterified isoidide is separated from a mixture containing the non-esterified isoidide obtained in step M4) and one or both compounds selected from the group consisting of esterified isosorbide and esterified isomannide, preferably by phase separation, and more preferably by liquid-liquid extraction. Steps to obtain and / or isolate non-esterified isoidides. The method according to any of the preceding embodiments, further including the method described above.

[0087] A8. The following additional steps (multiple steps are possible): M6) A step in which a mixture is used that comprises one or both compounds selected from the group consisting of esterified isosorbide and esterified isomannide, preferably an esterified isoidide obtained after separation in step M5), and / or further comprising one or more reaction products thereof, preferably one or more reaction products comprising one or more compounds selected from the group consisting of isosorbide, isomannide, and mixtures thereof, preferably further comprising isoidide. Preferably, one or more steps include providing or preparing a mixture of the compound of formula II in step M3), and / or M7) is a step of hydrolyzing a mixture comprising one or both compounds selected from the group consisting of esterified isosorbide and esterified isomannide, preferably further comprising the esterified isoidide obtained after separation in step M5), Preferably, the step further includes using the isosorbide and / or isomannide thus obtained in step M2), The method according to any of the preceding embodiments.

[0088] A9. A composition comprising a mixture, preferably as described in embodiment A1 or A4, comprising a non-esterified isoidide and one or both compounds selected from the group consisting of esterified isosorbide and esterified isomannide.

[0089] A10. - The molar ratio of the non-esterified isoidide present in the composition to the total of the esterified isoidide, esterified isosorbide, and esterified isomannide present in the composition is in the range of 40:60 to 65:35, preferably in the range of 45:55 to 60:40. and / or - The molar ratio of non-esterified isoidide to esterified isoidide present in the composition is in the range of 75:25 to 98:2, preferably in the range of 80:20 to 95:5. and / or - The molar ratio of non-esterified isosorbide present in the composition to esterified isosorbide present is in the range of 20:80 to 0.01:99.99, preferably in the range of 5:95 to 0.5:99.5. and / or - The molar ratio of the non-esterified isomannide present in the composition to the esterified isomannide present is in the range of 20:80 to 0.01:99.99, preferably in the range of 5:95 to 0.1:99.9. and / or - The composition comprises isoidide, isomannide-2,5-diacetate, and isosorbide monoacetate, preferably isosorbide-5-monoacetate. The composition according to embodiment 9.

[0090] A11. A composition according to any one of embodiments A9 to A10, which can be obtained or obtained by the method described in any one of embodiments A1 to A8.

[0091] A12. - In a method for producing and / or isolidides, preferably as a starting material or intermediate, and / or - A method for separating isoidides from other dianhydrohexitols, preferably from a mixture of other dianhydrohexitols or dianhydrohexitol isomers containing isosorbide and / or isomannide, Preferably as a starting material or intermediate, Use of the composition described in any of embodiments A9 to A11.

[0092] A13. Use of a method comprising the step of selective esterification of a mixture of dianhydrohexitol isomers containing an isoidide, preferably the method according to any one of embodiments A1 to A8, for separating the isoidide from the mixture of dianhydrohexitol isomers, preferably from the mixture of compounds of formula II as defined in embodiment A1 or A3.

[0093] A14. The use according to embodiment A13, wherein the method comprises the step of selectively esterifying a dianhydrohexitol isomer other than an isoidide, followed by the step of separating the non-esterified isoidide from the mixture of esterified dianhydrohexitol isomers.

[0094] A15. A method for producing a polymer comprising an isoidide monomer or a modified isoidide monomer, comprising producing or isolating the isoidide monomer and / or modified isoidide monomer by any of the methods of embodiments A1 to A8, or by a method comprising any of the methods of embodiments A1 to A8.

[0095] [Examples] The following embodiments of the present invention are intended to further illustrate and illustrate the present invention without limiting its scope.

[0096] [Example 1] Isomerization of isosorbide using Ru / C as a transition metal catalyst (Step M2) A solution of isosorbide (10.00 g, 68.4 mM) in isopropanol (20 mL) was stirred in a reactor for 2 hours under a hydrogen pressure of 10 bar (1000 kPa) and a temperature of 220 °C ("mobile hydrogenation conditions") with 500 mg of 5% Ru / C heterogeneous catalyst (5% by mass Ru / C catalyst, yielding 0.25% by mass ruthenium relative to the mass of isosorbide used). The reactor was then cooled to room temperature and the pressure was reduced. The catalyst (Ru / C) was isolated by filtration (this revealed a catalyst recovery rate of over 97%) and washed with fresh isopropanol (10 mL). The filtrate (containing organic components) was concentrated under reduced pressure to obtain a colorless, viscous oily substance containing a mixture of dianhydrohexitols. This oily substance was characterized by the different dianhydrohexitol components (confirmed by gas chromatography combined with mass spectrometry, GC-MS). 1 (By relative integration of the 1H-NMR signals), it was found that the mixture contains isoidide (55 mol% of the total molar amount of dianhydrohexitol present in the mixture), isosorbide (38 mol% of the total molar amount of dianhydrohexitol present in the mixture), and isomannide (7 mol% of the total molar amount of dianhydrohexitol present in the mixture).

[0097] Next, the colorless, viscous oily substance obtained from this reaction was used in the following reaction step without further purification or isolation of its components.

[0098] [Example 2] Selective esterification of a mixture of compounds of formula II (steps M3) and M4)) - Part I To the colorless, viscous oily substance (containing isoidide, isosorbide, and isomannide; step M3)) obtained in Example 1 above, acetic anhydride (7.12 mL, 75.3 mM) and lead(II) acetate (556 mg, 1.71 mM) were added, and the resulting mixture was stirred at room temperature for 3 hours. Then, ethyl acetate (30 mL) was added to the mixture to precipitate the lead(II) acetate catalyst. The precipitated catalyst was subsequently collected by filtration (which revealed a catalyst recovery rate of over 96%) and washed with fresh ethyl acetate (5 mL).

[0099] Next, the combined ethyl acetate phase obtained from this reaction (containing a mixture of esterified, specifically acetylated, dianhydrohexitol and unesterified dianhydrohexitol) was used in the following reaction step without further purification or isolation of its components.

[0100] [Example 3] Separation of isoidides from a mixture of dianhydrohexitols by liquid-liquid extraction (Step M5) - Part I The combined ethyl acetate phase obtained in Example 2 (containing a mixture of esterified, specifically acetylated, dianhydrohexitol and unesterified dianhydrohexitol) was stirred with water (30 mL) for 30 minutes, then the layers were separated, and the aqueous layer was extracted with ethyl acetate four times (4 × 30 mL), with the aqueous phase and the ethyl acetate phase being stirred again for 30 minutes before each separation in each case.

[0101] The aqueous phase was subsequently separated, and water was removed under reduced pressure to produce an isoidide (4.21 g, 42% of the total amount of isosorbide used as a starting material in Example 1).

[0102] The purity of the isoidide obtained in this Example 3 was determined by gas chromatography (GC-MS) combined with mass spectrometry, and 1 Analysis using 1H-NMR revealed that the percentage was over 99%.

[0103] [Example 4] Hydrolysis of esterified dianhydrohexitol (Step M7) The organic (ethyl acetate) phase from Example 3 (containing a mixture of esterified, specifically acetylated, dianhydrohexitol) was combined, and the solvent was removed from the combined organic phase under reduced pressure to produce a colorless oily substance (7.21 g).

[0104] The resulting oily substance was dissolved in water (15 mL), and an acidic cation exchange resin (Amberlite® IR120, 1.0 g) was added. The resulting mixture was heated under reflux for 6 hours. After the mixture cooled to room temperature, the acidic cation exchange resin was collected by filtration (the recovery rate of the acidic cation exchange resin was found to be over 99%), and the filtrate was concentrated under reduced pressure to produce a mixture of isosorbide, isomannide, and isoidide (molar ratio of isomers: 69 (isosorbide): 13 (isomannide): 18 (isooidide), total yield: 5.21 g). The ratio of isomers in the mixture was determined to reflect the characteristics of each different dianhydrohexitol component. 1 The signal was determined by relative integration of the H-NMR signals.

[0105] In this Example 4, the mixture of isosorbide, isomannide, and isoidide thus obtained was recycled and used in step M2) of the method for producing and / or isolating isoidide according to the present invention (see Example 5 below).

[0106] [Example 5] Recirculation of the dianhydrohexitol mixture obtained in step M7) The mixture of isosorbide, isomannide, and isoidide obtained in Example 4 above was subjected to step M2) using the procedure described in Example 1 above to obtain a mixture containing isoidide (55 mol% of the total molar amount of dianhydrohexitol present in the mixture), isosorbide (38 mol% of the total molar amount of dianhydrohexitol present in the mixture), and isomannide (7 mol% of the total molar amount of dianhydrohexitol present in the mixture).

[0107] [Example 6] Isomerization of isosorbide using Raney nickel as a transition metal catalyst (Step M2) A solution of isosorbide (1.00 g, 6.84 mmol) in isopropanol (10 mL) was stirred in a reactor for 3 hours under a hydrogen pressure of 10 bar (1000 kPa) and a temperature of 200°C ("mobile hydrogenation conditions") with a Raney nickel catalyst (100 mg, "Grace 3202", containing over 92% Ni) accelerated at 1 mass% Mo. The reactor was then cooled to room temperature and the pressure was reduced. The catalyst (Raney nickel) was isolated by filtration (which revealed a catalyst recovery rate of over 99%) and washed with fresh isopropanol (10 mL). The filtrate (containing organic components) was concentrated under reduced pressure to obtain a colorless, viscous oily substance containing a mixture of dianhydrohexitols. This oily substance contained the characteristic features of different dianhydrohexitol components. 1 Based on relative integration of 1H-NMR signals and GC-MS, it was found that the mixture contains isoidide (54 mol% of the total molar amount of dianhydrohexitol in the mixture), isosorbide (39 mol% of the total molar amount of dianhydrohexitol in the mixture), and isomannide (7 mol% of the total molar amount of dianhydrohexitol in the mixture).

[0108] Next, the colorless, viscous oily substance obtained from this reaction was used in the following reaction step without further purification or isolation of its components.

[0109] [Example 7] Selective esterification of a mixture of compounds of formula II (steps M3 and M4) - Part II In Example 6, to the colorless, viscous oily substance prepared according to the method described above (1.0 g, 6.84 mM; containing isoidide, isosorbide, and isomannide in the molar ratios shown above in Example 6), a carboxylic acid anhydride (8.21 mM; in all cases, the carboxylic acid anhydride identified in Examples 8a to 8f in Table 1 below) and lead(II) acetate trihydrate (65 mg, 0.171 mM) were added, and the resulting mixture was stirred at room temperature for 3 hours in all cases. Then, ethyl acetate (5 mL) was added to the mixture, and in all cases, the lead(II) acetate catalyst was precipitated. The precipitated catalyst was subsequently collected by filtration and washed with fresh ethyl acetate (2 mL).

[0110] Next, the combined ethyl acetate phase obtained from this reaction (containing a mixture of esterified, specifically acylated, dianhydrohexitol and unesterified dianhydrohexitol) was used in the following reaction step without further purification or isolation of these components.

[0111] [Example 8] Separation of isoidides from a mixture of dianhydrohexitols by liquid-liquid extraction (Step M5) - Part II The combined ethyl acetate phase (containing a mixture of esterified, specifically acylated, dianhydrohexitol and unesterified dianhydrohexitol) obtained in Example 7 (obtained from several experiments; see Table 1 below) was evaporated under reduced pressure to obtain an oily residue in each case. Each of these oily residues was then dissolved in water (15 mL) and extracted six times (6 × 15 mL) with ethyl acetate using a separatory funnel.

[0112] In both cases, water is subsequently removed from the aqueous phase under reduced pressure, and in both cases, the remaining organic residue is removed. 1 Analysis was performed using 1H-NMR and GC-MS. The absolute yield (in g) of each organic residue and the results of these analyses are shown in Table 1, Examples 8a-8f below:

[0113] [Table 1]

[0114] In Table 1 above, "composition" refers to the composition of the obtained organic residue in all cases, and the "mol%" shown for "composition" in Table 1 is the mol% of the components of the composition relative to the total molar amount of dianhydrohexitol (including acylated dianhydrohexitol) present in the obtained organic residue.

[0115] From the data shown in Table 1, it can be generally concluded that anhydrides of carboxylic acids having a total number of carbon atoms of 5 or less, in particular, enable particularly efficient liquid-liquid extraction with low loss and in the desired yield. However, when anhydrides of carboxylic acids having a larger total number of carbon atoms are used, the cost of the reagent is higher. Pivalic acid anhydride and isobutyric acid anhydride (both containing branched carbon chains) showed the most favorable results in terms of the yield of the isoidide thus obtained and the purity of the isoidide. Therefore, it can be further concluded that symmetric anhydrides of carboxylic acids having a total number of carbon atoms of 5 or less, preferably symmetric anhydrides of carboxylic acids having a total number of carbon atoms in the range of 2 to 5 (preferably where the present carbon atoms (where structurally possible) form branched carbon chains), are particularly preferred as reagents for the reaction with a mixture of compounds of formula II in step M4 of the method for producing and / or isolating isoidides according to the present invention. Examples of embodiments of the present invention include the following. [Embodiment 1] Equation I [ka] A method for producing and / or isoliding the isoidide of, The following steps: M3) Formula II comprising one or both compounds selected from the group consisting of isoidides, isosorbides, and isomannides. [ka] A step of preparing or making a mixture of the compounds, Step M4) is to subject the mixture of compounds of formula II from step M3) to selective esterification conditions so that a mixture comprising one or both compounds selected from the group consisting of non-esterified isoidides, esterified isosorbides, and esterified isomannides is obtained. Selective esterification is - Performed in the presence of a metal catalyst, and - The process involves reacting a compound mixture of formula II with a reagent selected from the group consisting of carboxylic acid anhydrides, wherein the carboxylic acid(s) forming the carboxylic acid anhydride are selected from the group consisting of carboxylic acids containing a total number of carbon atoms ranging from 2 to 8. Step, and Step M5) Separating the non-esterified isoidide from the mixture obtained in step M4) containing one or both compounds selected from the group consisting of esterified isosorbide and esterified isomannide, thereby obtaining and / or isolating the non-esterified isoidide. Methods that include... [Embodiment 2] The selective esterification in step M4) - This is carried out by selectively esterifying isosorbide and / or isomannide in the presence of isoizide. and / or - This was carried out in the presence of a metal catalyst. The metal is selected from the group consisting of calcium, strontium, barium, zinc, cadmium, mercury, indium, thallium, lanthanides, tin, lead, antimony, bismuth, iron, cobalt, and nickel. Preferably, this is carried out in the presence of a metal salt catalyst. Preferably, the metal is selected from the group consisting of calcium, strontium, barium, zinc, cadmium, mercury, indium, thallium, lanthanides, tin, lead, antimony, bismuth, iron, cobalt, and nickel. and / or - The operation is carried out at temperatures in the range of -20°C to 50°C, preferably in the range of 10°C to 50°C, more preferably in the range of 15°C to 45°C, and even more preferably in the range of 15°C to 35°C. and / or - The reaction is carried out with a reaction time ranging from 15 minutes to 24 hours, preferably from 30 minutes to 10 hours, more preferably from 1 hour to 5 hours, and more preferably from 1 hour to 3 hours. The method according to Embodiment 1. [Embodiment 3] The method according to Embodiment 1 or 2, wherein the selective esterification in step M4) is carried out in the presence of a metal catalyst, the metal catalyst being or comprising a lead catalyst, preferably a lead salt catalyst. [Embodiment 4] The mixture of compounds of formula II prepared or made in step M3) includes or comprises isoidide, isosorbide and isomannide, Preferably - The isoidide is present in a total amount of 10 to 95 mol%, preferably 40 to 95 mol%, and more preferably 50 to 90 mol%, relative to the total molar amount of the mixture of compounds of formula II. or - The isoidide is present in a total amount of 40 to 70 mol%, preferably 45 to 65 mol%, and more preferably 50 to 60 mol%, relative to the total molar amount of the mixture of compounds of formula II. The method according to any one of Embodiments 1 to 3. [Embodiment 5] - In a mixture obtained in step M4) comprising a non-esterified isoidide and one or both compounds selected from the group consisting of esterified isosorbide and esterified isomannide, - The molar ratio of non-esterified isoidide to esterified isoidide is in the range of 75:25 to 98:2, preferably in the range of 80:20 to 95:5. and / or - The molar ratio of the present non-esterified isosorbide to the present esterified isosorbide is in the range of 20:80 to 0.01:99.99, preferably in the range of 5:95 to 0.5:99.5. and / or - The molar ratio of the present non-esterified isomannide to the present esterified isomannide is in the range of 20:80 to 0.01:99.99, preferably in the range of 5:95 to 0.1:99.9. and / or - The mixture obtained in step M4) contains a non-esterified isoidide and one or both compounds selected from the group consisting of esterified isosorbide and esterified isomannide, and preferably contains isoidide, isomannide-2,5-diacetate and isosorbide monoacetate, preferably isosorbide-5-monoacetate. The method according to any one of Embodiments 1 to 4. [Embodiment 6] The following additional steps: M2) One or more compounds selected from the group consisting of isosorbide, isomannide, isosorbide esters, isomannide esters, and mixtures thereof. Preferably, one or more compounds selected from the group consisting of isosorbide, isomannide, and mixtures thereof, more preferably isosorbide. Preferably, one or more compounds selected from the group consisting of isosorbide, isomannide, and mixtures thereof are used as a mixture of organic hydroxyl compounds, containing a total amount of isosorbide in the range of 90 to 99.5% by mass, preferably 95 to 99.5% by mass, relative to the total mass of sorbitol, mannitol, isosorbide, isomannide, and sorbitan derivatives (selected from the group consisting of 1,4-sorbitan, 3,6-sorbitan, 2,5-mannitan, 2,6-sorbitan, 1,5-sorbitan, 2,5-iditan, and mixtures thereof) present in the mixture of organic hydroxyl compounds. Under conditions of mobile hydrogenation in the presence of a transition metal catalyst and preferably in the presence of hydrogen, Preferably in the presence of a polar solvent selected from the group consisting of alcohols, water, and mixtures thereof, The step of reacting the compounds to obtain a compound mixture of formula II as described in Embodiment 1 or 4. The method described in any of Embodiments 1 to 5, preferably Embodiment 4, including the method described in Embodiment 4. [Embodiment 7] The following additional steps: M1) A step of reacting one or both compounds selected from the group consisting of sorbitol, mannitol, and mixtures thereof under acidic conditions to obtain one or more compounds selected from the group consisting of isosorbide, isomannide, and mixtures thereof. Preferably, this is used in step M2) to obtain one or more compounds selected from the group consisting of isosorbide, isomannide, and mixtures thereof. The method according to embodiment 6, including the method described in embodiment 6. [Embodiment 8] Step M5) M5) The non-esterified isoidide is separated from the mixture obtained in step M4) which contains the non-esterified isoidide and one or both compounds selected from the group consisting of esterified isosorbide and esterified isomannide, by phase separation, preferably by liquid-liquid extraction. Steps to obtain and / or isolate non-esterified isoidides. The method according to any one of embodiments 1 to 7, including the method described above. [Embodiment 9] The following additional steps (multiple steps are possible): M6) A step in which a mixture is used that comprises one or both compounds selected from the group consisting of esterified isosorbide and esterified isomannide, preferably further comprising the esterified isoidide obtained after separation in step M5) and / or one or more reaction products thereof, preferably one or more reaction products comprising one or more compounds selected from the group consisting of isosorbide, isomannide, and mixtures thereof, preferably further comprising isoidide. Preferably, in one or more steps, a mixture of the compound of formula II of step M3) is provided or prepared, and / or M7) is a step of hydrolyzing a mixture comprising one or both compounds selected from the group consisting of esterified isosorbide and esterified isomannide, preferably further comprising the esterified isoidide obtained after separation in step M5), The method according to any one of Embodiments 1 to 8, further comprising the step of using the isosorbide and / or isomannide thus obtained in step M2, preferably. [Embodiment 10] Preferably, a composition comprising a mixture containing a non-esterified isoidide and one or both compounds selected from the group consisting of esterified isosorbide and esterified isomannide, as described in Embodiment 1 or 5. [Embodiment 11] The composition according to Embodiment 10, wherein the present esterified isosorbide, present esterified isomannide, and present esterified isoidide are esterified with a carboxylic acid containing a total number of carbon atoms in the range of 2 to 8. [Embodiment 12] - The molar ratio of the non-esterified isoidide present in the composition to the total of the esterified isoidide, esterified isosorbide, and esterified isomannide present in the composition is in the range of 40:60 to 65:35, preferably in the range of 45:55 to 60:40. and / or - The molar ratio of non-esterified isoidide to esterified isoidide present in the composition is in the range of 75:25 to 98:2, preferably in the range of 80:20 to 95:5. and / or - The molar ratio of non-esterified isosorbide present in the composition to esterified isosorbide present is in the range of 20:80 to 0.01:99.99, preferably in the range of 5:95 to 0.5:99.5. and / or - The molar ratio of the non-esterified isomannide present in the composition to the esterified isomannide present is in the range of 20:80 to 0.01:99.99, preferably in the range of 5:95 to 0.1:99.9. and / or - The composition comprises isoidide, isomannide-2,5-diacetate, and isosorbide monoacetate, preferably isosorbide-5-monoacetate. The composition according to Embodiment 10 or 11. [Embodiment 13] The composition according to Embodiment 11, wherein the molar ratio of non-esterified isoidide to esterified isoidide present in the composition is in the range of 75:25 to 98:2, preferably in the range of 80:20 to 95:5. [Embodiment 14] A composition according to any one of embodiments 10 to 13, which can be obtained or obtained by the method described in any one of embodiments 1 to 9. [Embodiment 15] - In a method for producing and / or isolidides, preferably as a starting material or intermediate, and / or - In a method for separating isoidides from other dianhydrohexitols, preferably from a mixture of other dianhydrohexitols or dianhydrohexitol isomers containing isosorbide and / or isomannide, preferably as a starting material or intermediate, Use of the composition described in any of Embodiments 10 to 14. [Embodiment 16] The use of the method of any one of Embodiments 1 to 9, comprising the step of selective esterification of the mixture of dianhydrohexitol isomers containing the isoidide, preferably from the mixture of compounds of formula II as described in Embodiment 1 or 4. [Embodiment 17] The use according to Embodiment 16, wherein the method comprises the step of selectively esterifying a dianhydrohexitol isomer other than isoidide, followed by the step of separating the non-esterified isoidide from the mixture of esterified dianhydrohexitol isomers. [Embodiment 18] A method for producing a polymer comprising an isoidide monomer or a modified isoidide monomer, comprising producing or isolating the isoidide monomer and / or modified isoidide monomer by the method described in any of Embodiments 1 to 9, or by a method comprising the method described in any of Embodiments 1 to 9.

Claims

1. Equation I 【Chemistry 1】 A method for producing and / or isoliding the isoidide of, The following steps: M3) Formula II comprising isoidide and one or more compounds selected from the group consisting of isosorbide and isomannide 【Chemistry 2】 A step of preparing or making a mixture of the compounds, M4) A step in which a mixture of compounds of formula II from step M3) is subjected to selective esterification conditions so as to obtain a mixture comprising a non-esterified isoidide and one or more compounds selected from the group consisting of esterified isosorbide and esterified isomannide, Selective esterification is - Performed in the presence of a metal catalyst, and - The process involves reacting a compound mixture of formula II with a reagent selected from the group consisting of carboxylic acid anhydrides, wherein the carboxylic acid or carboxylic acid(s) forming the carboxylic acid(s) or carboxylic acid(s) forming the carboxylic acid anhydride(s) is selected from the group consisting of carboxylic acids containing a total number of carbon atoms ranging from 2 to 8. Step, and Step M5) Separating the non-esterified isoidide from a mixture containing the non-esterified isoidide obtained in step M4) and one or more compounds selected from the group consisting of esterified isosorbide and esterified isomannide, thereby obtaining and / or isolating the non-esterified isoidide. Methods that include...

2. The selective esterification in step M4) - This was carried out in the presence of a metal salt catalyst. The metal is selected from the group consisting of calcium, strontium, barium, zinc, cadmium, mercury, indium, thallium, lanthanides, tin, lead, antimony, bismuth, iron, cobalt, and nickel. The method according to claim 1.

3. The selective esterification in step M4) is carried out at a temperature in the range of -20°C to 50°C. The method according to claim 1 or 2.

4. The selective esterification in step M4) is carried out for a reaction time in the range of 15 minutes to 24 hours. The method according to any one of claims 1 to 3.

5. The method according to any one of claims 1 to 4, wherein the selective esterification in step M4) is carried out in the presence of a lead salt catalyst.

6. The method according to any one of claims 1 to 5, wherein the mixture of compounds of formula II prepared or made in step M3) includes or comprises isoidide, isosorbide and isomannide.

7. - The isoidide is present in a total amount ranging from 40 to 95 mol% relative to the total molar amount of the mixture of compounds of formula II. The method according to claim 6.

8. - The isoidide is present in a total amount in the range of 40 to 70 mol% relative to the total molar amount of the mixture of compounds of formula II. The method according to claim 6 or 7.

9. - In a mixture obtained in step M4) comprising a non-esterified isoidide and one or more compounds selected from the group consisting of esterified isosorbide and esterified isomannide, - The molar ratio of non-esterified isoidide to esterified isoidide is in the range of 75:25 to 98:

2. The method according to any one of claims 1 to 8.

10. - A mixture comprising a non-esterified isoidide obtained in step M4) and one or more compounds selected from the group consisting of esterified isosorbide and esterified isomannide, - The molar ratio of existing non-esterified isosorbide to existing esterified isosorbide is in the range of 20:80 to 0.01:99.

99. The method according to any one of claims 1 to 9.

11. - A mixture comprising a non-esterified isoidide obtained in step M4) and one or more compounds selected from the group consisting of esterified isosorbide and esterified isomannide, - The molar ratio of the present non-esterified isomannide to the present esterified isomannide is in the range of 20:80 to 0.01:99.

99. The method according to any one of claims 1 to 10.

12. - A mixture comprising a non-esterified isoidide obtained in step M4) and one or more compounds selected from the group consisting of esterified isosorbide and esterified isomannide, - A mixture obtained in step M4) containing a non-esterified isoidide and one or more compounds selected from the group consisting of esterified isosorbide and esterified isomannide contains isoidide, isomannide-2,5-diacetate and isosorbide monoacetate. The method according to any one of claims 1 to 11.

13. The following additional steps: M2) A step of reacting one or more compounds selected from the group consisting of isosorbide, isomannide, isosorbide esters, isomannide esters, and mixtures thereof, in the presence of a transition metal catalyst and under conditions of mobile hydrogenation in the presence of hydrogen, to obtain a mixture of compounds of formula II as described in claim 1 or 6. The method according to any one of claims 1 to 12, including the method described in any one of claims 1 to 12.

14. The method according to claim 13, wherein in step M2), one or more compounds are selected from the group consisting of isosorbide, isomannide, and mixtures thereof.

15. The method according to claim 14, wherein one or more compounds selected from the group consisting of isosorbide, isomannide, and mixtures thereof are used as a mixture of organic hydroxyl compounds, and the mixture of organic hydroxyl compounds contains a total amount of isosorbide in the range of 90 to 99.5% by mass, relative to the total mass of sorbitol, mannitol, isosorbide, isomannide, and sorbitan derivatives present in the mixture of organic hydroxyl compounds, wherein the sorbitan derivative is selected from the group consisting of 1,4-sorbitan, 3,6-sorbitan, 2,5-mannitan, 2,6-sorbitan, 1,5-sorbitan, 2,5-iditan, and mixtures thereof.

16. To obtain one or more compounds selected from the group consisting of isosorbide, isomannide, and mixtures thereof, which will be used in step M2), The following additional steps: M1) A step of reacting at least one substance selected from the group consisting of sorbitol, mannitol, and mixtures thereof under acidic conditions to obtain one or more compounds selected from the group consisting of isosorbide, isomannide, and mixtures thereof. The method according to any one of claims 13 to 15, including the method described in any one of claims 13 to 15.

17. Step M5) M5) Separating the non-esterified isoidide from the mixture obtained in step M4) by liquid-liquid separation, which includes the non-esterified isoidide and at least one compound selected from the group consisting of esterified isosorbide and esterified isomannide, to obtain and / or isolate the non-esterified isoidide. The method according to any one of claims 1 to 16, including the method described in any one of claims 1 to 16.

18. The following additional steps: M6) In order to provide or prepare a mixture of the compound of formula II in step M3), a step is taken in which a mixture is used that includes one or more compounds selected from the group consisting of esterified isosorbide and esterified isomannide obtained after separation in step M5), The method according to any one of claims 1 to 17, further comprising:

19. The following additional steps: The method according to any one of claims 1 to 18, further comprising the step of hydrolyzing a mixture containing one or more compounds selected from the group consisting of esterified isosorbide and esterified isomannide obtained after separation in step M5), wherein the isosorbide and / or isomannide thus obtained in step M2) is used.

20. A composition comprising a mixture containing a non-esterified isoidide and one or more compounds selected from the group consisting of esterified isosorbide and esterified isomannide, Existing esterified isosorbides, esterified isomannides, and esterified isoidides are esterified with carboxylic acids containing a total number of carbon atoms ranging from 2 to 8. A composition in which the molar ratio of non-esterified isoidide to esterified isoidide present in the composition is in the range of 75:25 to 98:

2.

21. - The molar ratio of the non-esterified isoidide present in the composition to the total of the esterified isoidide, esterified isosorbide, and esterified isomannide present in the composition is in the range of 40:60 to 65:

35. The composition according to claim 20.

22. - The molar ratio of non-esterified isoidide to esterified isoidide present in the composition is in the range of 80:20 to 95:

5. The composition according to claim 20 or 21.

23. - The molar ratio of the non-esterified isosorbide present in the composition to the esterified isosorbide present is in the range of 20:80 to 0.01:99.

99. The composition according to any one of claims 20 to 22.

24. - The molar ratio of the non-esterified isomannide present in the composition to the esterified isomannide present is in the range of 20:80 to 0.01:99.

99. The composition according to any one of claims 20 to 23.

25. - The composition comprises isoizide, isomannide-2,5-diacetate and isosorbide monoacetate, The composition according to any one of claims 20 to 24.

26. - In a method for producing and / or isolidides, as a starting material or intermediate, Use of the composition according to any one of claims 20 to 25.

27. - In a method for separating isoidides from other dianhydrohexitols or mixtures of dianhydrohexitol isomers containing isosorbide and / or isomannide, as a starting material or intermediate, Use of the composition according to any one of claims 20 to 25.

28. The method according to any one of claims 1 to 19, comprising the step of selective esterification of a mixture of dianhydrohexitol isomers containing an isoidide for separating the isoidide from the mixture of dianhydrohexitol isomers.

29. The method according to claim 28, comprising the steps of selectively esterifying a dianhydrohexitol isomer other than an isoidide, followed by separating the non-esterified isoidide from the mixture of esterified dianhydrohexitol isomers.

30. A method for producing a polymer comprising an isoidide monomer or a modified isoidide monomer, comprising producing or isolating the isoidide monomer and / or a modified isoidide monomer by the method described in any one of claims 1 to 19, or by a method comprising the method described in any one of claims 1 to 19.

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