# US 10,246,407 B2 · Process for preparing biphenylamines from anilides by ruthenium catalysis

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- Number: US 10,246,407 B2
- Document ID: US10246407B2
- Status: Granted
- Kind: B2
- Application number: 15/305,865
- Filed: 2015-04-22
- Published: 2017-02-16
- Granted: 2019-04-02
- Earliest claimed: 2014-04-25
- Assignees: Bayer CropScience AG
- Applicants: Bayer Cropscience Aktiengesellschaft
- Inventors: Thomas Himmler; Lars Rodefeld; Jonathan Hubrich; Lutz Ackermann
- Web page: https://patentgrep.com/patent/US10246407B2

## CPC

- C07C 231/12: by reactions not involving the formation of carboxamide groups
- C07C: ACYCLIC OR CARBOCYCLIC COMPOUNDS

## Abstract

The present invention relates to a novel process for preparing substituted biphenylamides of the general formula (V) characterized in that anilides of the formula (II) in a solvent other than tetrahydrofuran, are reacted with an organoboron compound of the formula (III) in the presence of a catalyst system consisting of a ruthenium catalyst, an activator, an oxidizing agent and a metal triflate.

## Claims

### Claim 1

A process for the preparation of one or more biphenylamides of formula (V)
wherein
R1 is hydrogen, hydroxyl, fluorine, chlorine, C1-C4-alkyl, C1-C4-alkoxy, C1-C4-alkylthio or C1-C4-haloalkyl,
R2 is C1-C4-alkyl, C6-C10-aryl or C6-C10-aryl-CH2—, and
X1 is hydrogen, C1-C4-alkyl, C1-C4-alkoxy, fluorine or chlorine,
X2 is hydrogen, C1-C4-alkyl, C1-C4-alkoxy, fluorine or chlorine,
X3 is hydrogen, C1-C4-alkyl, C1-C4-alkoxy, fluorine or chlorine,
comprising reacting one or more anilides of formula (II)
wherein
R1 and R2 are each as defined above,
in a solvent selected from the group consisting of N,N-dialkylalkanamides, dimethoxyethane (DME), methanol, ethyl acetate, water, and mixtures of these solvents,
with an organoboron compound of formula (III)
wherein
X1, X2 and X3 are each as defined above, and which is selected from one of the following groups consisting of:
(i) boronic acids of formula (III) in which
Q is a hydroxyl group,
m is 2, and
p is 1,
or the anhydrides, dimers or trimers of these boronic acids;
(ii) boronic acid derivatives of formula (III) in which
Q is F, C1, Br, I, C1-C4-alkyl, C6-C10-aryl, C1-C4-alkoxy or C6-C10-aryloxy,
m is 2, and
p is 1;
(iii) borinic acids of formula (III) in which
Q is OH, F, C1, Br, I, C1-C4-alkyl, C6-C10-aryl, C1-C4-alkoxy or C6-C10-aryloxy,
m is 1, and
p is 2;
(iv) cyclic boronic esters of formula (III) in which
Q is a C2-C3-alkyldioxy radical which, together with the boron atom to which it is bonded, forms a 5- or 6-membered ring optionally substituted by one or more C1-C4-alkyl radicals,
m is 1, and
p is 1;
(v) boronates of formula (III) in which
Q is OH, F, C1, Br, I, C1-C4-alkyl, C6-C10-aryl, C1-C4-alkoxy or C6-C10-aryloxy,
m is 3, and
p is 1
and the negative charge of the boronate anion is compensated for by a cation,
(vi) triarylboranes of formula (III) in which
m is 0, and
p is 3; and
(vii) tetraarylborates of formula (III) in which
m is 0, and
p is 4
and the negative charge of the tetraarylborate anion is compensated for by a cation,
in the presence of a catalyst system consisting of a ruthenium catalyst, an activator, an oxidizing agent and a metal triflate.

### Claim 2 (depends on 1)

A process according to claim 1, wherein an amide of formula (V) is deprotected in a second stage to give a free amine of formula (I)

### Claim 3 (depends on 1)

A process according to claim 1, wherein the solvent is selected from the group consisting of N,N-dialkylalkanamides and mixtures of these thereof.

### Claim 4 (depends on 1)

A process according to claim 1, wherein the catalyst is [{RuCl2(p-cymene)}2].

### Claim 5 (depends on 1)

A process according to claim 1, wherein the oxidizing agent is Ag2O.

### Claim 6 (depends on 1)

A process according to claim 1, wherein the metal of the metal triflate is selected from the group consisting of Li, Na, K, Mg, Ca, Mn, Fe, Co, Ni, Cu and Zn.

### Claim 7 (depends on 1)

A process according to claim 1, wherein the metal of the metal triflate is selected from the group consisting of sodium, potassium, manganese, zinc, iron and nickel.

### Claim 8 (depends on 1)

A process according to claim 1, wherein the activator is selected from the group consisting of AgSbF6, KPF6, NaPF6, AgF and AgBF4.

### Claim 9 (depends on 1)

A process according to claim 1, wherein the organoboron compound of formula (III) is a boronic acid of formula (III), group (i), wherein Q=OH, m=2 and p=1.

### Claim 10 (depends on 1)

A process according to claim 1, wherein the organoboron compound of formula (III) is a boronic acid of formula (III), group (i), wherein Q=OH, m=2 and p=1, the solvent is DMF, the catalyst is [{RuCl2(p-cymene)}2], the metal triflate is iron(III) triflate, the oxidizing agent is Ag2O and the activator is AgSbF6.

### Claim 11 (depends on 1)

A process according to claim 1, wherein the organoboron compound of formula (III) is a boronic acid of formula (III), group (i), in which
Q is a hydroxyl group,
m is 2, and
p is 1,
or an anhydride, dimer or trimer thereof.

### Claim 12 (depends on 1)

A process according to claim 1, wherein the organoboron compound of formula (III) is a boronic acid derivative of formula (III), group (ii), in which
Q is F, C1, Br, I, C1-C4-alkyl, C6-C10-aryl, C1-C4-alkoxy or C6-C10-aryloxy,
m is 2, and
p is 1.

### Claim 13 (depends on 1)

A process according to claim 1, wherein the organoboron compound of formula (III) is a borinic acid of formula (III), group (iii), in which
Q is OH, F, C1, Br, I, C1-C4-alkyl, C6-C10-aryl, C1-C4-alkoxy or C6-C10-aryloxy,
m is 1, and
p is 2.

### Claim 14 (depends on 1)

A process according to claim 1, wherein the organoboron compound of formula (III) is a cyclic boronic ester of formula (III), group (iv), in which
Q is a C2-C3-alkyldioxy radical which, together with the boron atom to which it is bonded, forms a 5- or 6-membered ring optionally substituted by one or more C1-C4-alkyl radicals,
m is 1, and
p is 1.

### Claim 15 (depends on 1)

A process according to claim 1, wherein the organoboron compound of formula (III) is a boronate of formula (III), group (v), in which
Q is OH, F, Cl, Br, I, C1-C4-alkyl, C6-C10-aryl, C1-C4-alkoxy or C6-C10-aryloxy,
m is 3, and
p is 1,
and the negative charge of the boronate anion is compensated for by a cation.

### Claim 16 (depends on 1)

A process according to claim 1, wherein the organoboron compound of formula (III) is a triarylborane of formula (III), group (vi), in which
m is 0, and
p is 3.

### Claim 17 (depends on 1)

A process according to claim 1, wherein the organoboron compound of formula (III) is a tetraarylborate of formula (III), group (vii), in which
m is 0, and
p is 4,
and the negative charge of the tetraarylborate anion is compensated for by a cation.

### Claim 18 (depends on 1)

A process according to claim 1, wherein the solvent is water.

### Claim 19 (depends on 1)

A process according to claim 1, wherein the solvent is dimethylformamide (DMF).

### Claim 20 (depends on 1)

A process according to claim 1, wherein the solvent is N-methylpyrrolidone (NMP).