Process for producing arylamines

Patent metadata

Field	Value
Publication number	US-9499474-B2
Application number	US-201214357374-A
Country	US
Kind code	B2
Filing date	Oct 19, 2012
Priority date	Nov 11, 2011
Publication date	Nov 22, 2016
Grant date	Nov 22, 2016

Abstract

The invention relates to a process for producing compounds containing at least one arylamino group by means of a coupling reaction of an amino compound with an aryl compound, using a strong base.

First claim

The invention claimed is:

1. A process for the preparation of a compound containing at least one arylamino group, the process comprising at least one palladium-catalysed coupling reaction between an amino compound, and an aryl compound, Ar—(X) n , in the presence of a base having a pK a value based on dimethyl sulfoxide of at least 33, the process indicated by the following reaction scheme

and the amino compound is of the formula

wherein:
Ar is an aromatic ring system having 10 to 30 aromatic ring atoms, optionally substituted by one or more radicals R 1 , and includes a condensed aromatic ring system of at least two aromatic rings condensed with one another, where the one ring is condensed onto the other ring in an ortho-position to the bond to the amine nitrogen;
E is, identically or differently on each occurrence, selected from a single bond, C(R 1 ) 2 , C═O, Si(R 1 ) 2 , NR 1 , O, and S;
R is, identically or differently on each occurrence, selected from H, a straight-chain alkyl group having 1 to 20 C atoms or a branched or cyclic alkyl group having 3 to 20 C atoms or an alkenyl or alkynyl group having 2 to 20 C atoms, optionally substituted by one or more radicals R 1 and where one or more CH 2 groups in the above-mentioned groups are optionally replaced by —R 1 C═CR 1 —, —C≡C—, Si(R 1 ) 2 , C═O, C═S, C═NR 1 , —C(═O)O—, —C(═O)NR 1 —, NR 1 , P(═O)(R 1 ), —O—, —S—, SO, or SO 2 , and where one or more H atoms in the above-mentioned groups are optionally replaced by D, F, Cl, Br, I, CN or NO 2 , or an aryl group having 5 to 60 aromatic ring atoms, optionally substituted by one or more radicals R 1 ,
where at least one R is an aryl group with a substituent R 1 in the ortho-position to the bond to the nitrogen atom, or at least one R is an aryl group with a condensed-on ring in the ortho-position to the bond to the nitrogen atom, and
where radicals R are optionally linked to one another to define a ring, and where not more than one group R on a nitrogen atom is equal to H;

R 1 is, identically or differently on each occurrence, selected from H, D, F, Cl, Br, I, B(OR 2 ) 2 , CHO, C(═O)R 2 , CR 2 ═C(R 2 ) 2 , CN, C(═O)OR 2 , C(═O)N(R 2 ) 2 , Si(R 2 ) 3 , N(R 2 ) 2 , NO 2 , P(═O)(R 2 ) 2 , OSO 2 R 2 , OR 2 , S(═O)R 2 , S(═O) 2 R 2 , a straight-chain alkyl, alkoxy or thioalkyl group having 1 to 20 C atoms or a branched or cyclic alkyl, alkoxy or thioalkyl group having 3 to 20 C atoms or an alkenyl or alkynyl group having 2 to 20 C atoms, each optionally substituted by one or more radicals R 2 and where one or more CH 2 groups in the above-mentioned groups are optionally replaced by —R 2 C═CR 2 —, —C≡C—, Si(R 2 ) 2 , C═O, C═S, C═NR 2 , —C(═O)O—, —C(═O)NR 2 —, NR 2 , P(═O)(R 2 ), —O—, —S—, SO, or SO 2 , and where one or more H atoms in the above-mentioned groups are optionally replaced by D, F, Cl, Br, I, CN or NO 2 , or an aromatic ring system having 5 to 30 aromatic ring atoms, which may in each case be substituted by one or more radicals R 2 , or an aryloxy group having 5 to 30 aromatic ring atoms, optionally substituted by one or more radicals R 2 , where two or more radicals R 1 are optionally linked to one another to define a ring;
R 2 is, identically or differently on each occurrence, H, D, F, or an aliphatic, aromatic, or heteroaromatic organic radical having 1 to 20 C atoms, wherein one or more H atoms are optionally replaced by D or F; two or more substituents R 2 are optionally linked to one another to define a ring;
X is, identically or differently on each occurrence, a leaving group;
k is, identically or differently on each occurrence, 0 or 1, wherein, if k=zero, the group E is not present; and
n is a value of 1 to 10.

2. The process of claim 1 , wherein the base has a pK a value that is greater than the pK a value of the amino compound by at least 6.

3. The process of claim 1 , wherein the base has a pK a value based on dimethyl sulfoxide of at least 34.

4. The process of claim 1 , wherein the base has a pK a value based on dimethyl sulfoxide of at least 36.

5. The process of claim 1 , wherein the base is selected from amides with alkali-metal or alkaline-earth metal counterion and organometallic compounds containing a formally negatively charged carbon atom with alkali-metal or alkaline-earth metal counterion.

6. The process of claim 1 , wherein the amino compound is a diarylamino compound.

7. The process of claim 1 , wherein all groups R are not H.

8. The process of claim 1 , wherein n is 1 or 2.

9. The process of claim 1 , wherein the group Ar contains at least one radical R 1 in the ortho-position to the bond to the leaving group X which is other than H and D.

10. The process of claim 1 , wherein the group Ar includes a condensed aryl group selected from naphthalene, anthracene, phenanthrene, pyrene, chrysene, perylene, fluoranthene, benzanthracene, benzophenanthrene, tetracene, pentacene, benzopyrene, acridine, or phenanthridine.

11. The process of claim 10 , wherein the group Ar further includes an aromatic ring system selected from fluorene, spirobifluorene, cis- or trans-indenofluorene, cis- or trans-indolocarbazole, cis- or trans-indenocarbazole, cis- or trans-monobenzindenofluorene, and cis- or trans-dibenzindenofluorene.

12. The process of claim 1 , wherein a crude product yield is of greater than 80% of the compound containing at least one arylamino group, and less than 20% of by-products selected from a defunctionalisation or coupling of the base.

13. A process for the preparation of a compound containing at least one arylamino group, the process comprising at least one palladium-catalysed coupling reaction between a diarylamino compound, and an aryl compound, Ar—(X) n , in the presence of a base having a pK a value of at least 36, based on dimethyl sulfoxide, and the pK a value of the base is greater than the pK a value of the amino compound by at least 6, the process indicated by the following reaction scheme

and the amino compound is of formula

wherein:
Ar is an aromatic ring system having 10 to 30 aromatic ring atoms, optionally substituted by one or more radicals R 1 , and includes a condensed aromatic ring system of at least two aromatic rings condensed with one another, where the one ring is condensed onto the other ring in an ortho-position to the bond to the amine nitrogen;
E is, identically or differently on each occurrence, selected from a single bond, C(R 1 ) 2 , C═O, Si(R 1 ) 2 , NR 1 , O, and S;
R is, identically or differently on each occurrence, selected from H, a straight-chain alkyl group having 1 to 20 C atoms or a branched or cyclic alkyl group having 3 to 20 C atoms or an alkenyl or alkynyl group having 2 to 20 C atoms, optionally substituted by one or more radicals R 1 and where one or more CH 2 groups in the above-mentioned groups are optionally replaced by —R 1 C═CR 1 —, —C≡C—, Si(R 1 ) 2 , C═O, C═S, C═NR 1 , —C(═O)O—, —C(═O)NR 1 —, NR 1 , P(═O)(R 1 ), —O—, —S—, SO, or SO 2 , and where one or more H atoms in the above-mentioned groups are optionally replaced by D, F, Cl, Br, I, CN or NO 2 , or an aryl group having 5 to 60 aromatic ring atoms, optionally substituted by one or

Assignees

• Merck Patent Gmbh

Inventors

• Kaufhold Oliver
• Spreitzer Hubert
• Riedmueller Stefan

Classifications

• C07C209/10 Primary

  with formation of amino groups bound to carbon atoms of six-membered aromatic rings or from amines having nitrogen atoms bound to carbon atoms of six-membered aromatic rings · CPC title

• C07C211/61

  with at least one of the condensed ring systems formed by three or more rings · CPC title

• C07C2603/54

  containing more than five condensed rings · CPC title

• C07C2103/54

  Chemistry & Metallurgy · mapped topic