# US 9,751,841 B2 · Process for the preparation of chalcogene compounds

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- Number: US 9,751,841 B2
- Document ID: US9751841B2
- Status: Granted
- Kind: B2
- Application number: 13/263,192
- Filed: 2010-03-30
- Published: 2012-05-03
- Granted: 2017-09-05
- Earliest claimed: 2009-04-06
- Assignees: Petroliam Nasional Berhad
- Applicants: Robin Don Rogers; John Holbrey; Hector Rodriguez
- Inventors: Robin Don Rogers; John Holbrey; Hector Rodriguez
- Web page: https://patentgrep.com/patent/US9751841B2

## CPC

- C07D 233/42: Sulfur atoms
- Y02P 20/582: Recycling of unreacted starting or intermediate materials
- C07D: HETEROCYCLIC COMPOUNDS (macromolecular compounds C08)
- Y02P: CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS

## Abstract

The present invention is a novel process for the preparation of chalcogenone compounds by conversion of ionic liquids and salts comprising nitrogen-containing heterocyclic cations and basic anions to the corresponding nitrogen-containing heterocyclic chalcogenones by reaction with elemental chalcogens.

## Claims

### Claim 1

A process for the preparation of heterocyclic chalcogenone compounds comprising the reaction of an elemental chalcogen selected from the group consisting of elemental sulfur, elemental selenium and elemental tellurium with an ionic liquid or salt having the formula:
[Cat+][X−],
wherein: [Cat+] represents one or more heterocyclic cationic species of the general formula (1) having adjacent carbon and nitrogen atoms:
wherein
Ra represents a C1 to C30 straight chain or branched alkyl group, a C3 to C8 cycloalkyl group, a C6 to C10 aryl group, a C1 to C30 alkaryl group, or a C1 to C30 aralkyl group; wherein said alkyl, cycloalkyl, aryl, alkaryl or aralkyl groups are unsubstituted or substituted; and
Q represents a linking moiety, which may be saturated or unsaturated, and which may be substituted or unsubstituted; and which when taken together with the adjacent carbon and nitrogen atoms forms a heterocyclic ring comprising 5 to 10 ring atoms; and
[X−] represents one or more anionic species selected from conjugate bases of acids [H+X−] having a pKa value greater than 2.5; and
wherein the reaction is conducted in the absence of an additional base.

### Claim 2 (depends on 1)

The process according to claim 1, wherein the elemental chalcogen is selected from the group consisting of elemental selenium and elemental sulfur.

### Claim 3 (depends on 2)

The process according to claim 2, wherein the elemental chalcogen is elemental sulfur.

### Claim 4 (depends on 1)

The process according to claim 1, wherein general formula (1) represents a heterocyclic cationic ring structure selected from the group consisting of imidazolium, pyrazolium, 1,2,4-triazolium, oxazolium, isoxazolium, thiazolium, isothiazolium, 1,2,4-oxadiazolium, 1,2,5-oxadiazolium, 1,3,4-oxadiazolium, 1,2,3,4-oxatriazolium, 1,2,3,5-oxatriazolium, 1,2,4-thiadiazolium, 1,2,5-thiadiazolium, 1,3,4-thiadiazolium, 1,2,3,4-thiatriazolium, 1,2,3,5-thiatriazolium, pyridinium, pyridazinium, pyrimidinium, pyrazinium, 1,2,3-triazinium, 1,2,4-triazinium, 1,3,5-triazinium, 1H-indazolium, benzimidazolium, benzisoxazolium, benzoxazolium, benzothiazolium, benzisothiazolium, quinolinium, isoquinolinium, cinnolinium, quinazolinium, quinoxalinium, and phthalazinium.

### Claim 5 (depends on 4)

The process according to claim 4, wherein general formula (1) represents a heterocyclic cationic ring structure selected from the group consisting of imidazolium, pyrazolium, 1,2,4-triazolium, oxazolium, thiazolium, pyridinium, pyridazinium, pyrimidinium, pyrazinium, benzimidazolium, quinolinium, and isoquinolinium.

### Claim 6 (depends on 5)

The process according to claim 5, wherein general formula (1) represents a heterocyclic cationic ring structure selected from the group consisting of
wherein: Ra, Rb, Rc, Rd, Re, Rf, Rg and Rh are each independently selected from the group consisting of a C1 to C30, straight chain or branched alkyl group, a C3 to C8 cycloalkyl group, a C6 to C10 aryl group, C1 to C30 alkaryl group, a C1 to C30 aralkyl group, and wherein Rb, Rc, Rd, Re, Rf and Rh may also be hydrogen or C1 to C30 alkoxy, or any two of Rb, Rc, Rd, Re, Rf and Rh attached to adjacent carbon atoms may form a methylene chain —(CH2)q— wherein q is from 3 to 6; and wherein said alkyl, cycloalkyl, aryl, alkaryl, aralkyl or alkoxy groups or said methylene chain are unsubstituted or may be substituted by one to three groups selected from the group consisting of C1 to C6 alkoxy, C2 to C12 alkoxyalkoxy, C3 to C8 cycloalkyl, C6 to C10 aryl, C7 to C10 alkaryl, C7 to C10 aralkyl, —CN, —OH, —SH, —NO2, —CO2(C1 to C6)alkyl, —OC(O)Rx, —C(O)Rx, —C(S)Rx, —CS2(C1 to C6)alkyl, —SC(S)Rx, —S(O)(C1 to C6)alkyl, —S(O)O(C1 to C6)alkyl, —OS(O)(C1 to C6)alkyl, —S(C1 to C6)alkyl, —S—S(C1 to C6 alkyl), —NRxC(O)NRyRz, —NRxC(O)O(C1 to C6)alkyl, —OC(O)NRyRz, —NRxC(S)O(C1 to C6)alkyl, —OC(S)NRyRz, —NRxC(S)S(C1 to C6)alkyl, —SC(S)NRyRz, —NRxC(S)NRyRz, —C(O)NRyRz, —C(S)NRyRz, —NRyRz, and a heterocyclic group, wherein Rx, Ry and Rz are independently selected from the group consisting of hydrogen and C1 to C6 alkyl.

### Claim 7 (depends on 6)

The process according to claim 6, wherein general formula (1) represents a heterocyclic cationic ring structure selected from the group consisting of
wherein: Ra, Rb, Rc, Rd, Re, Rf, Rg are as defined in claim 6.

### Claim 8 (depends on 6, 7)

A process according to claim 7, wherein general formula (1) represents a heterocyclic cationic ring structure selected from the group consisting of
wherein: Ra and Rg are as defined in claim 6.

### Claim 9 (depends on 1)

The process according to claim 1, wherein [X−] comprises the anionic conjugate base of an acid [H+X−]having a pKa value greater than 3.5.

### Claim 10 (depends on 1)

A process according to claim 1, wherein [X−] comprises the anionic conjugate base of an acid [H+X−] having a pKa value greater than 4.5.

### Claim 11 (depends on 1)

The process according to claim 1, wherein [X−] comprises a carboxylate anion.

### Claim 12 (depends on 11)

The process according to claim 11, wherein [X−] comprises a carboxylate anion selected from the group consisting of [CH3CO2]−, [CH3CH2CO2]−, [CH3(CH2)2CO2]−,and [PhCO2]−.

### Claim 13 (depends on 11)

The process according to claim 11, wherein [X−] comprises an anion selected from the group consisting of [CN]−, [CO3]2−, [HCO3]−, [OH]−, [SH]−, and [NO2]−.

### Claim 14 (depends on 1)

The process according to claim 1, wherein the reaction is conducted at a temperature of from −10° C. to 150° C.

### Claim 15 (depends on 14)

The process according to claim 14, wherein the reaction is conducted at a temperature of from 25° C. to 100° C.

### Claim 16 (depends on 1)

The process according to claim 1, wherein the salt has a melting point below 150° C.

### Claim 17 (depends on 16)

The process according to claim 16, wherein the salt has a melting point below 100° C.

### Claim 18 (depends on 17)

The process according to claim 17, wherein the salt has a melting point below 25° C.

### Claim 19 (depends on 1)

The process according to claim 1, wherein the salt is a solid at the operating temperature and pressure of the process.

### Claim 20 (depends on 1)

The process according to claim 1, wherein the reaction is conducted in the presence of a solvent selected from the group consisting of acetonitrile, dimethylsulfoxide, dimethylformamide and sulfolane.

### Claim 21 (depends on 1)

The process according to claim 1, wherein the reaction is conducted in the absence of an additional solvent.

### Claim 22 (depends on 1)

The process according to claim 1, wherein the acid [H+X−] is a by-product that is continuously removed from the reaction vessel.

### Claim 23 (depends on 1)

The process according to claim 1, wherein the ionic liquid or salt and the chalcogen are reacted in a molar ratio, based on atoms of the chalcogen, of from 1:100 to 100:1.

### Claim 24 (depends on 23)

The process according to claim 23, wherein the ionic liquid or salt and the chalcogen are reacted in a molar ratio, based on atoms of the chalcogen, of from 1:10 to 10:1.

### Claim 25 (depends on 24)

The process according to claim 24, wherein the ionic liquid or salt and the chalcogen are reacted in a molar ratio, based on atoms of the chalcogen, of from 1:5 to 5:1.

### Claim 26 (depends on 25)

The process according to claim 25, wherein the ionic liquid or salt and the chalcogen are reacted in a molar ratio, based on atoms of the chalcogen, of about 1:1.

### Claim 27 (depends on 1)

The process according to claim 1, wherein the chalcogenone product is recovered from the reaction medium by solvent extraction using aqueous and/or organic solvents.