Intermolecular reaction of propargyl ethers with dimethylfuran in the presence of gold(I) complexes

Patent metadata

Field	Value
Publication number	US-10815178-B2
Application number	US-201916720580-A
Country	US
Kind code	B2
Filing date	Dec 19, 2019
Priority date	Dec 21, 2015
Publication date	Oct 27, 2020
Grant date	Oct 27, 2020

Abstract

The present invention relates to a method of preparing ortho substituted phenols from 2,5-dimethylfuran and propargyl ethers in the presence of a gold(I) complex. It is particularly advantageous to use 2,5-dimethylfuran as this offers an ecological beneficial synthesis of said ortho substituted phenols.

First claim

The invention claimed is:

1. A process which comprises:
(i) producing a compound of formula (I):

wherein R 1 represents a C 1-10 -alkyl group or a C 4-7 -cycloalkyl group by reacting in the presence of a gold(I) complex a compound of formula (II):

with compound of formula (III):

(ii) reducing the compound of formula (I) by a reducing agent in the presence of a heterogeneous metal catalyst to yield a compound of formula (A):

wherein the metal is selected from the group consisting of Ni, Fe, Ir, Pd, Pt, Rh and Ru.

2. The process according to claim 1 , wherein R 1 represents a C 1-6 -alkyl group.

3. The process according to claim 1 , wherein the gold(I) complex has the formula:
[Au(I)OL]AN
wherein OL represents an organic ligand and AN represents a single charged anion.

4. The process according to claim 1 , wherein the gold(I) complex has a single charged anion (AN) which is selected from the group consisting of [BX 4 ] − , [PX 6 ] − , [SbF 6 ] − , [ClO 4 ] − , —CF 3 COO − , a sulfonate of formula (AN-II), tetra(3,5-bis(trifluoromethyl)phenyl)borate (BAr F − ), tetraphenylborate, and anions of formula (AN-I):

wherein
X represents a halogen atom; and
Y 1 represents a phenyl or a C 1-8 -alkyl group which optionally is substituted by at least one halogen atom.

5. The process according to claim 1 , wherein the gold(I) complex has an organic ligand (OL) which is either
(i) at least one phosphorous containing ligand which is selected from the group consisting of formula (P1), (P2), (P3), (P4), (P5), (P6), (P7) and (P8);
(ii) at least an imidazole-2-ylidene ligand compound of formula (IM): or
(iii) at least a 1H-1,2,3-triazol ligand of formula (TR-1), or (TR-2) or (TR-3):

wherein
R 10 and R 11 represent independently from each other either H or a linear or branched C 1-10 -alkyl or C 4-10 -cycloalkyl group; and wherein
R 12 , R 13 , R 14 and R 15 represent independently from each other H or a linear or branched C 1-6 -alkyl group;
n stands for an integer of 1-6, and
n′ stands for 0, 1 or 2.

6. The process according to a claim 1 , wherein the gold(I) complex is prepared from a gold(I) chloro complex and a silver(I) salt.

7. The process according to claim 6 wherein 1 the gold (I) complex is of formula:
[Au(I)OL]AN
wherein OL represents an organic ligand and AN represents a single charged anion, and
wherein the gold (I) complex is a reaction product of Au(I)OLCl and AgAN.

8. The process according to claim 1 , wherein the gold (I) complex is of formula:
[Au(I)OL]AN
wherein OL represents an organic ligand and AN represents a single charged anion, and
wherein the gold (I) complex is a reaction product of Au(I)OLCl and NaAN.

9. The process according to claim 1 , wherein step (i) comprises:
ia) separating the compound of formula (I) from a compound of formula (IVa) and/or formula (IVb):

wherein the wavy line represents a carbon-carbon bond which is linked to the adjacent carbon-carbon double bond so as to have the said carbon-carbon double bond either in a the Z or in an the E-configuration.

10. The process according to claim 9 , wherein step (ia) comprises separating the compound of formula (I) from the compound of formula (IVa) and/or (IVb) are by chromatography.

11. A process for the manufacture of a compound of formula (C) from a compound of formula (I), wherein the process comprises the following steps of:
a′) reducing the compound of formula (I) by the process according to claim 1 to yield a compound of formula (A):

b′) oxidizing the compound of formula (A) by an oxidizing agent to yield a compound of formula (B):

c′) and thereafter reducing the compound of formula (B) by a reducing agent to yield a compound of formula (C):

12. A process for the manufacture of a compound of formula (D) from a compound of formula (I) comprising the steps:
a′) hydrogenating a compound of formula (I) by the process according to claim 1 to yield compound of formula (A):

b′) oxidizing the compound of formula (A) by an oxidizing agent to yield a compound of formula (B):

c′) reducing the compound of formula (B) by a reducing agent to yield a compound of formula (C):

d′) and thereafter condensing isophytol with the compound of formula (C) to yield a compound of formula (D):

Assignees

• Dsm Ip Assets Bv

Inventors

• Letinois Ulla
• Ackermann Stephan
• Medlock Jonathan Alan
• Lehmann Hajo

Classifications

• C07C43/1783

  with hydroxy or -O-metal groups bound to the aromatic rings · CPC title

• C07C37/07

  with simultaneous reduction of C=O group in that ring · CPC title

• C07C41/30 Primary

  by increasing the number of carbon atoms, e.g. by oligomerisation · CPC title

• C07C46/08

  with molecular oxygen · CPC title

• B01J31/183

  with more than one complexing nitrogen atom, e.g. phenanthroline · CPC title