2,2′-diaminobiaryls having a phthaloyl group or succinoyl group

Patent metadata

Field	Value
Publication number	US-10131628-B2
Application number	US-201515507970-A
Country	US
Kind code	B2
Filing date	Jul 23, 2015
Priority date	Sep 3, 2014
Publication date	Nov 20, 2018
Grant date	Nov 20, 2018

Abstract

An electrochemical treatment of differently protected aniline or napthylamine results in the preparation of unsymmetrical 2, 2′-diaminebiaryls provided with different protecting groups. The treatment involves the protecting groups prior to the C, C coupling step. The co-reactants generally have different oxidation potentials which results from the selection of the protecting groups. The treatment also enables controlled access to the individual amino functions of the 2, 2′-diaminobiaryls by subsequent selective deprotection.

First claim

The invention claimed is:

1. A process for preparing 2,2′-diaminobiaryls, comprising:
a1) reacting a compound of the formula (IVa) or (Va):

with reaction of (IVa) with X 21 to give (IVb), or
reaction of (Va) with X 22 to give (Vb):

b1) reacting a compound of the formula (VIa) or (VIIa):

with reaction of (VIa) with X 23 to give (VIb), or
reaction of (VIIa) with X 24 to give (VIIb):

c1) electrochemical coupling of:
(IVb) with (VIb) to give (VIII) or
(IVb) with (VIIb) to give (IX) or
(Vb) with (VIIb) to give (X),

in each case in a reaction mixture where the compound having the higher oxidation potential is present in excess:

where
R 5′ , R 6′ , R 7′ , R 8′ , R 9′ , R 10′ are selected from the group consisting of —H, —(C 1 -C 12 )-alkyl, —O—(C 1 -C 12 )-alkyl, and —O—(C 6 -C 20 )-aryl;
R 11 , R 12 , R 13 , R 14 , 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 1 -C 12 )-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 8 -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 , 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 21 , X 22 , X 23 , X 24 are selected from the group consisting of:

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

with reaction of (IVa) with X 21 to give (IVb), or
reaction of (Va) with X 22 to give (Vb), or
reaction of (VIIa) with X 24 to give (VIIb):

b2) reacting a compound of the formula (VIa), (VIa) or (VIIa):

with reaction of (IVa) with X 5 to give (IVc), or
reaction of (VIa) with X 6 to give (VIc), or
reaction of (VIIa) with X 7 to give (VIIc):

c2) electrochemical coupling of:
(IVb) with (VIc) to give (XI) or
(IVb) with (VIIc) to give (XII) or
(IVc) with (VIIb) to give (XIII) or
(Vb) with (VIIc) to give (XIV),

in each case in a reaction mixture where the compound having the higher oxidation potential is present in excess:

where
R 5′ , R 6′ , R 7′ , R 8′ , R 9′ , R 10′ are selected from the group consisting of —H, —(C 1 -C 12 )-alkyl, —O—(C 1 -C 12 )-alkyl, and —O—(C 6 -C 20 )-aryl;
R 11 , R 12 , R 13 , R 14 , 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 , 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 2 )-alkyl, —CO—(C 1 -C 12 )-alkyl, —CO—(C 6 -C 2 )-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 5 , X 6 , X 7 are selected from:
tert-butyloxycarbonyl, methyloxycarbonyl, benzyloxycarbonyl, phenyloxycarbonyl, acetyl, trifluoroacetyl, benzoyl, sulphonyl, sulphenyl;
X 21 , X 22 , X 24 are selected from the group consisting of:

Assignees

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

Inventors

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

Classifications

• C07C311/21 Primary

  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

• C07C217/84

  the oxygen atom of at least one of the etherified hydroxy groups being further bound to an acyclic carbon atom · CPC title

• C25B11/12

  Chemistry & Metallurgy · mapped topic

• C25B3/10

  Chemistry & Metallurgy · mapped topic

• 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