Preparation of 2,6- and 2,7-disubstituted anthraquinone derivates

Patent metadata

Field	Value
Publication number	US-10227281-B2
Application number	US-201515315143-A
Country	US
Kind code	B2
Filing date	May 28, 2015
Priority date	May 30, 2014
Publication date	Mar 12, 2019
Grant date	Mar 12, 2019

Abstract

A composition comprising a compound of formula (Va) wherein n is 1 or 2 and wherein m is 1 or 2, with n and m preferably both being 1 or both being 2, more preferably both being 1, and/or, preferably and, a compound of formula, wherein n is 1 or 2 and wherein m is 1 or 2, with n and m preferably both being 1 or both being 2, more preferably both being 1, and wherein at least 90 weight-% of the composition consist of compounds of formula (Va) and formula (Vb).

First claim

The invention claimed is:

1. A process for the preparation of an anthraquinone derivative, the process comprising:
(i) providing a mixture (A) comprising: a compound of formula (I)

a compound of formula (II)

wherein x is 1, or a compound of formula (II) wherein x is 2, or a mixture of a compound of formula (II) wherein x is 1 and a compound of formula (II) wherein x is 2, a dehydrogenation catalyst, and a liquid solvent system;

(ii) treating the mixture (A) with an oxygen-containing gas obtaining a mixture (B) comprising a compound of formula (IIIa)

and/or, a compound of formula (IIIb)

wherein, in each of formula (IIIa) and (IIIb), n is 1 or 2 and wherein, in each of formula (IIIa) and (IIIb), m is 1 or 2; and

(iii) treating the mixture (B), optionally after work-up, with an oxygen-containing gas, obtaining a mixture (C) comprising a compound of formula (IVa)

and/or a compound of formula (IVb)

wherein, in each of formula (IVa) and (IVb), n is 1 or 2 and wherein, in each of formula (IVa) and (IVb), m is 1 or 2.

2. The process of claim 1 , wherein
the mixture (A) provided in (i) comprises a compound of formula (II) wherein x is 1 and the mixture (B) obtained in (ii) comprises a compound of formula (IIIa) and a compound of formula (IIIb) wherein n is 1 and m is 1, and the mixture (C) obtained in (iii) comprises a compound of formula (IVa) and a compound of formula (IVb) wherein n is 1 and m is 1; or
wherein the mixture (A) provided in (i) comprises a compound of formula (II) wherein x is 2 and the mixture (B) obtained in (ii) comprises a compound of formula (IIIa) and a compound of formula (IIIb) wherein n is 2 and m is 2, and the mixture (C) obtained in (iii) comprises a compound of formula (IVa) and a compound of formula (IVb) wherein n is 2 and m is 2.

3. The process of claim 1 , wherein the sequence of (i) to (iii) is carried out as a one-pot process.

4. The process of claim 1 , wherein the dehydrogenation catalyst according to (i) comprises at least one element selected from the group consisting of palladium, platinum, copper, lithium, zinc, zirconium, and aluminum.

5. The process of claim 1 , wherein said providing the mixture (A) according to (i) comprises admixing the compound of formula (I) with the compound of formula (II) at a molar ratio of the compound of formula (I) relative to the compound of formula (II) in the range of from 0.1:1 to 0.5:1.

6. The process of claim 1 , wherein the liquid solvent system according to (i) comprises at least one organic solvent selected from the group consisting of benzene, monoalkylated benzene, polyalkylated benzene, an alkyl phosphate, an alkylcyclohexanol ester, a N,N-dialkyl carbonamide, a N-alkyl carbonamide, a N-aryl carbonamide, a N,N-dialkyl carbamate, a tetraalkyl urea, a cycloalkyl urea, a phenylalkyl urea, a N-alkyl-2-pyrrolidone, a N-alkyl caprolactam, and an alcohol.

7. The process of claim 6 , wherein the liquid solvent system according to (i) further comprises water, wherein in the liquid solvent system, the molar ratio of organic solvent relative to water is in the range of from 1:1 to 5:1.

8. The process of claim 1 , wherein prior to (ii), the process further comprises heating the mixture (A) to a temperature in the range of from 40 to 75° C.

9. The process of claim 1 , wherein the providing according to (i) comprises:
(i.1) preparing a mixture (A.1) comprising at least a portion of the dehydrogenation catalyst and at least a portion of the liquid solvent system;
(i.2) adding at least a portion of the compound of formula (I) and at least a portion of the compound of formula (II) to the mixture (A.1) prepared in (i.1);
wherein prior to (i.2), the mixture (A.1) is heated to a temperature in the range of from 40 to 75° C.

10. The process of claim 1 , wherein in (ii), the treating of mixture (A) with the oxygen-containing gas is carried out for a period of time in the range of from 0.1 to 240 h, and is carried out by passing the oxygen-containing gas through the mixture (A), and wherein
the oxygen-containing gas is at least one member selected from the group consisting of oxygen, air, and lean air.

11. The process of claim 1 , wherein in (iii), the mixture (B) comprises water and is treated with the oxygen-containing gas after work-up, the work-up comprising separating at least a portion of the water from the mixture (B).

12. The process of claim 1 , wherein in (iii), the treating of mixture (B) with the oxygen-containing gas is carried out for a period of time in the range of from 0.1 to 150 h, and is carried out by passing the oxygen-containing gas through the mixture (B), wherein the oxygen-containing gas is at least one member selected from the group consisting of oxygen, air, and lean air.

13. The process of claim 1 , wherein the mixture B treated in (iii) comprises an inorganic base selected from the group consisting of potassium hydroxide, sodium hydroxide, and a combination thereof,
wherein the inorganic base is employed at a molar ratio of the inorganic base relative to compound of formula (I) in the range of from 0.1:1 to 1:1.

14. The process of claim 1 , further comprising:
(iv) separating the compound of formula (IVa), and/or the compound of formula (IVb) from the mixture (C), obtaining a mixture of which at least 95 weight-% consist of the compound of formula (IVa) and/or the compound of formula (IVb);
wherein (iv) comprises
(iv.1) extracting the mixture (C);
(iv.2) optionally drying the organic phase obtained from (iv.1), obtaining a solid;
(iv.3) admixing the organic phase obtained from (iv.1) or dissolving the solid obtained from (iv.2) with an organic solvent, at a temperature in the range of from 50 to 150° C., wherein the organic solvent is at least one member selected from the group consisting of benzene, monoalkylated benzene, polyalkylated benzene, an alkyl phosphate, an alkylcyclohexanol ester, a N,N-dialkyl carbonamide, a N-alkyl carbonamide, a N-aryl carbonamide, a N,N-dialkyl carbamate, a tetraalkyl urea, a cycloalkyl urea, a phenylalkyl urea, a N-alkyl-2-pyrrolidone, a N-alkyl caprolactam, and an alcohol having from 1 to 12 carbon atoms;
(iv.4) cooling the solution obtained from (iv.3) to temperature in the range of from −30 to +25° C., obtaining a suspension;
(iv.5) separating the solid from the suspension obtained from (iv.4);
(iv.6) optionally drying the solid obtained from (iv.5), wherein the drying can occur under vacuum;
(iv.7) optionally further purifying the solid obtained from (iv.5) or from (iv.6), wherein the further purifying can occur by chromatography.

15. The process of claim 14 , further comprising:
(v) subjecting at least one of the mixture obtained from (iii), the mixture obtained from (iv), and the solid obtained from (iv.6), to a hydrogenation reaction, in the presence of a hydrogenation catalyst, obtaining

Assignees

• Basf Se

Inventors

• Riedel Dominic
• Teles Joaquim Henrique
• Wurm Thomas

Classifications

• C07C37/14 Primary

  by addition reactions, i.e. reactions involving at least one carbon-to-carbon unsaturated bond · CPC title

• C07C50/20

  with unsaturation outside the ring system · CPC title

• C01B15/023

  by the alkyl-anthraquinone process · CPC title

• B01J21/04

  Alumina · CPC title

• C07C2521/06

  Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof · CPC title