Method for synthesising an unsaturated macrocyclic ketone

Patent metadata

Field	Value
Publication number	US-11021426-B2
Application number	US-201716758630-A
Country	US
Kind code	B2
Filing date	Oct 25, 2017
Priority date	Oct 25, 2017
Publication date	Jun 1, 2021
Grant date	Jun 1, 2021

Abstract

A method for producing unsaturated macrocyclic monoketones comprising the following steps: (a) preparing macrocyclic dienes with a ring size of at least 9 carbon atoms; (b) contacting the starting materials from step (a) with (b1) a palladium(II) salt and/or a palladium(II) complex; and (b2) an oxidant; and (b3) a solvent; and optionally (b4) a ligand; and optionally (b5) a co-catalyst; and optionally (b6) an acid.

First claim

The invention claimed is:

1. A method for preparing unsaturated macrocyclic monoketones comprising the following steps
(a) providing macrocyclic dienes having a ring size of at least 9 carbon atoms;
(b) contacting the starting materials from step (a) with
(b1) a palladium(II) salt and/or a palladium(II) complex; and
(b2) a bidenate ligand which contains N,N, N,O, N,S, or O,O donor atoms,
(b3) an oxidant; and
(b4) a solvent; and optionally
(b5) a cocatalyst; and optionally
(b6) an acid.

2. The method as claimed in claim 1 , wherein the solvent (b4) is a polar aprotic solvent and selected from the group consisting of N,N-disubstituted open-chain and cyclic acid amides, aliphatic, cycloaliphatic or aromatic nitriles, linear and cyclic ethers, cyclic carbonates, lactones, and mixtures thereof.

3. The method as claimed in claim 1 , wherein the palladium(II) salt and/or the palladium(II) complex (b1) are selected from the group consisting of palladium chloride, palladium bromide, H2PdCl4, Li2PdCl4, Na2PdCl4, K2PdCl4, (NH4)2PdCl4, palladium acetate, palladium trifluoroacetate, palladium benzoate, palladium nitrate, palladium sulfate tetrakis(acetonitrile)palladium(II) tetrafluoroborate, tetrakis(acetonitrile)palladium(II) bis(trifluoromethanesulfonate), and mixtures thereof.

4. The method as claimed in claim 1 , wherein the palladium(II) salt and/or the palladium(II) complex (b1) form with the bidentate ligand (b4) a palladium compound of the formula (I) and/or of the formula (II)

where X and Y each independently represent N,N, O,N or O,O; and
where Z each independently represent a halogen, acetate, trimethylacetate, trifluoromethylacetate, MeCN, PhCN, NO2, NO, nitrate, nitrite or sulfate;

where X and Y each independently represent O,O, N,N or O,N.

5. The method as claimed in claim 4 , wherein the palladium compound is added in a concentration from 0.01 to 25 mol % based on the starting material (a).

6. The method as claimed in claim 1 , wherein an oxygen-containing gas is used as the oxidant (b3).

7. The method as claimed in claim 6 , wherein the oxygen-containing gas contains oxygen in a concentration from 1% to 100% by volume.

8. The method as claimed in claim 1 , wherein the method is carried out at temperatures from 50° C. to 120° C.

9. The method as claimed in claim 1 , wherein the co-catalyst (b5) and the acid (b6) are mandatory.

10. The method as claimed in claim 9 , wherein the co-catalyst (b5) is selected from the group consisting of benzoquinones, naphthoquinones, anthraquinones, phosphomolybdic acid, phosphomolybdovanadic acids, phosphomolybdotungstic acids, phosphotungstovanadic acids, phthalocyanine complexes, FeSO4, CuCl, CuCl2, CuSO4, VOSO4, and mixtures thereof, and the acid (b6) is a Brønsted acid or Lewis acid.

11. The method as claimed in claim 10 , wherein the co-catalyst (b5) is added in a concentration from 1 to 300 mol %, based on the starting material (a).

12. The method as claimed in claim 10 , wherein the acid (b6) is added in a concentration from 5 to 500 mol % based on the starting material (a).

13. The method as claimed in claim 9 , wherein the palladium(II) salt and/or the palladium(II) complex (b1) is added in a concentration from 0.01 to 20 mol %, preferably from 0.5 to 10 mol %, and more preferably from 1 to 5 mol %, in each case based on the starting material (a).

14. The method as claimed in claim 10 , wherein the method is carried out at temperatures between 0° C.

15. The method of claim 1 , wherein the macrocyclic diene (a) has a ring size of from 12 to 30 carbon atoms.

16. The method of claim 1 , wherein the macrocyclic diene (a) has a ring size of from 12 to 18 carbon atoms.

Assignees

• Symrise Ag

Inventors

• Brunzel Tom
• Köckritz Angela
• Martin Andreas
• Trevino Diego A Jaime

Classifications

• B01J23/44

  Palladium · CPC title

• C07C2601/18

  with a ring being at least seven-membered · CPC title

• C07C45/34 Primary

  in unsaturated compounds · CPC title

• C07C49/587

  Unsaturated compounds containing a keto groups being part of a ring · CPC title

• B01J31/2226

  Anionic ligands, i.e. the overall ligand carries at least one formal negative charge · CPC title