2,2′-diaminobiaryls having one primary and one secondary amine

Patent metadata

Field	Value
Publication number	US-10125093-B2
Application number	US-201515507955-A
Country	US
Kind code	B2
Filing date	Jul 23, 2015
Priority date	Sep 3, 2014
Publication date	Nov 13, 2018
Grant date	Nov 13, 2018

Abstract

Novel 2,2′-diaminobiaryls having one primary and one secondary amine and an electrochemical process for preparation thereof.

First claim

The invention claimed is:

1. A process for preparing 2,2′-diaminobiaryls, comprising:
a2) reacting a compound of the formula (VIIa):

with X 12 to give (VIIb):

b2) reacting a compound of the formula (VIIIa):

with X 12′ to give (VIIIb):

c2) electrochemically coupling:
(VIIb) with (VIIIb) to give (IXa)
in a suitable electrolyte medium where the compound, (VIIb) or (VIIIb), having the higher oxidation potential is present in excess:

d2) selectively detaching X 12′ or X 12 , with conversion of (IXa) to (Xa) or (Xb):

where
R 11 , R 12 , R 13 , R 14 are selected from the group consisting of:
—H, —(C 1 -C 12 )-alkyl, —O—(C 1 -C 12 )-alkyl, —O—(C 6 -C 20 )-aryl, —(C 6 -C 20 )-aryl, —S-alkyl, —S-aryl, halogen, —COO—(C 1 -C 12 )-alkyl, —CONH—(C 1 -C 12 )-alkyl, —CO—(C 1 -C 12 )-alkyl, —CO—(C 6 -C 20 )-aryl, —COOH, —OH, —SO 3 H, —CN, and —N[(C 1 -C 12 )-alkyl] 2 ;
R 15′ , R 16′ , R 17′ , R 18′ , R 19′ , R 20′ are selected from the group consisting of:
—H, —(C 1 -C 12 )-alkyl, —O—(C 1 -C 12 )-alkyl, —O—(C 6 -C 20 )-aryl, —(C 6 -C 20 )-aryl, —S-alkyl, —S-aryl, halogen, —COO—(C 1 -C 12 )-alkyl, —CONH—(C 1 -C 12 )-alkyl, —CO—(C 1 -C 12 )-alkyl, —CO—(C 6 -C 20 )-aryl, —COOH, —OH, —SO 3 H, and —N[(C 1 -C 12 )-alkyl] 2 ;
where the alkyl and aryl groups mentioned may be substituted;
X 12 and X 12′ are selected from the group consisting of:
tert-butyloxycarbonyl, methyloxycarbonyl, benzyloxycarbonyl, phenyloxycarbonyl, acetyl, trifluoroacetyl, benzoyl, and sulphonyl, sulphenyl;
and X 12 is not the same radical as X 12′ .

Assignees

• Evonik Degussa Gmbh

Inventors

• Dyballa Katrin Marie
• Franke Robert
• Fridag Dirk
• Waldvogel Siegfried R
• Elsler Bernd
• Enders Mathias

Classifications

• C07C213/02

  by reactions involving the formation of amino groups from compounds containing hydroxy groups or etherified or esterified hydroxy groups · CPC title

• C07C311/21

  having the nitrogen atom of at least one of the sulfonamide groups bound to a carbon atom of a six-membered aromatic ring · CPC title

• C07C233/25

  having the carbon atom of the carboxamide group bound to a hydrogen atom or to a carbon atom of an acyclic saturated carbon skeleton · CPC title

• C07C303/40

  by reactions not involving the formation of sulfonamide groups · CPC title

• C07C231/12

  by reactions not involving the formation of carboxamide groups · CPC title