Process for preparing di-, tri- and polyamines by homogeneously catalyzed alcohol amination

Patent metadata

Field	Value
Publication number	US-RE46374-E
Application number	US-201615051391-A
Country	US
Kind code	E1
Filing date	Feb 23, 2016
Priority date	Mar 8, 2011
Publication date	Apr 25, 2017
Grant date	Apr 25, 2017

Abstract

Process for preparing primary amines which have at least one functional group of the formula (—CH 2 —NH 2 ) and at least one further primary amino group by alcohol amination of starting materials having at least one functional group of the formula (—CH 2 —OH) and at least one further functional group (—X), where (—X) is selected from among hydroxyl groups and primary amino groups, by means of ammonia with elimination of water, wherein the reaction is carried out homogeneously catalyzed in the presence of at least one complex catalyst comprising at least one element selected from groups 8, 9 and 10 of the Periodic Table and also at least one donor ligand.

First claim

The invention claimed is:

1. A process for preparing a primary amine comprising a functional group of formula (—CH 2 —NH 2 ) and a further primary amino group by alcohol amination, the process comprising reacting a starting material having a functional group of formula (—CH 2 —H) and a further functional group (—X), with ammonia with elimination of water,
wherein
(—X) is selected from the group consisting of a hydroxyl group and a primary amino group, and
the reacting is homogeneously catalyzed in the presence of a complex catalyst comprising an element selected from groups 8, 9 and 10 of the Periodic Table and also a donor ligand,
wherein the complex catalyst has formula I:

wherein
L 1 and L 2 are each independently selected from the group consisting of PR a R b , NR a R b , sulfide, SH, S(═O)R, C 5 -C 10 -heteroaryl comprising at least one heteroatom selected from the group consisting of N, O and S, AsR a R b , SbR a R b and an N-heterocyclic carbene of formula II or III:

L 3 is a monodentate two-electron donor selected from the group consisting of CO, PR a R b R c , NO + , AsR a R b R c , SbR a R b R c , SR a R b , RCN, RNC, N 2 , PF 3 , CS, pyridine, thiophene, tetrahydrothiophene and an N-heterocyclic carbene of formula II or III;
R 1 and R 2 are both hydrogen or together with carbon atoms to which they are bound form a phenyl ring which together with the quinolinyl unit of formula I forms an acridinyl unit;
R, R a , R b , R c , R 3 , R 4 and R 5 are each independently unsubstituted or at least monosubstituted C 1 -C 10 -alkyl, C 3 -C 10 -cycloalkyl, C 3 -C 10 -heterocyclyl comprising at least one heteroatom selected from the group consisting of N, O and S, C 5 -C 10 -aryl or C 5 -C 10 -heteroaryl comprising at least one heteroatom selected from the group consisting of N, O and S,
wherein substituents are selected from the group consisting of F, Cl, Br, OH, CN, NH 2 and C 1 -C 10 -alkyl;

Y is a monoanionic ligand selected from the group consisting of H, F, Cl, Br, I, OCOR, OCOCF 3 , OSO 2 R, OSO 2 CF 3 , CN, OH, OR and N(R) 2 , or an uncharged molecule selected from the group consisting of NH 3 , N(R) 3 and R 2 NSO 2 R;
X 1 represents one, two, three, four, five, six or seven substituents on an atom of the acridinyl unit or one, two, three, four or five substituents on an atom of the quinolinyl unit,
where plural X 1 are selected independently from the group consisting of hydrogen, F, Cl, Br, I, OH, NH 2 , NO 2 , —NC(O)R, C(O)NR 2 , —OC(O)R, —C(O)OR, CN, and a borane derivative that can be obtained from the catalyst of formula I by reaction with NaBH 4 , and unsubstituted or at least monosubstituted C 1 -C 10 -alkoxy, C 1 -C 10 -alkyl, C 3 -C 10 -cycloalkyl, C 3 -C 10 -heterocyclyl comprising a heteroatom selected from N, O and S, C 5 -C 10 -aryl and C 5 -C 10 -heteroaryl comprising at least one heteroatom selected from the group consisting of N, O and S,
wherein substituents are selected from the group consisting of F, Cl, Br, OH, CN, NH 2 and C 1 -C 10 -alkyl; and

M is iron, cobalt, nickel, ruthenium, rhodium, palladium, osmium, iridium or platinum.

2. The process according to claim 1 , wherein R 1 and R 2 are both hydrogen and the complex catalyst has formula (IV):

3. The process according to claim 1 , wherein R 1 and R 2 together with carbon atoms to which they are bound form a phenyl ring which together with the quinolinyl units of formula I forms an acridinyl unit and the complex catalyst has formula (V):

4. The process according to claim 1 , wherein the complex catalyst is selected from the group of catalysts of formulae (VI), (VII), (VIII), (IX), (X), (XI), (XII) and (XIII):

5. The process according to claim 1 , wherein the complex catalyst has formula (XIVa):

6. The process according to claim 1 , wherein the complex catalyst has formula (XIVb):

7. The process according to claim 1 , wherein the complex catalyst has formula (XV):

wherein
L 1 and L 2 are each independently selected from the group consisting of PR a R b , NR a R b , sulfide, SH, S(═O)R, C 5 -C 10 -heteroaryl comprising at least one heteroatom selected from the group consisting of N, O and S, AsR a R b , SbR a R b and an N-heterocyclic carbene of formula (II) or (III):

L 3 is a monodentate two-electron donor selected from the group consisting of CO, PR a R b R c , NO + , AsR a R b R c , SbR a R b R c , SR a R b , RCN, RNC, N 2 , PF 3 , CS, pyridine, thiophene, tetrahydrothiophene and an N-heterocyclic carbene of formula (II) or (III);
R 1 and R 2 are both hydrogen or together with carbon atoms to which they are bound form a phenyl ring which together with the quinolinyl unit of formula (XV) forms an acridinyl unit;
R, R a , R b , R c , R 3 , R 4 and R 5 are each independently unsubstituted or at least monosubstituted C 1 -C 10 -alkyl, C 3 -C 10 -cycloalkyl, C 3 -C 10 -heterocyclyl comprising at least one heteroatom selected from the group consisting of N, O and S, C 5 -C 10 -aryl or C 5 -C 10 -heteroaryl comprising at least one heteroatom selected from the group consisting of N, O and S,
wherein substituents are selected from the group consisting of: F, Cl, Br, OH, CN, NH 2 and C 1 -C 10 -alkyl; and

X 1 represents one, two, three, four, five, six or seven substituents on an atom of the acridinyl unit or one, two, three, four or five substituents on an atom of the quinolinyl unit,
where plural X 1 are selected independently from the group consisting of hydrogen, F, Cl, Br, I, OH, NH 2 , NO 2 , —NC(O)R, C(O)NR 2 , —OC(O)R, —C(O)OR, CN, a borane derivative that can be obtained from the catalyst of formula (XV) by reaction with NaBH 4 , and unsubstituted or at least monosubstituted C 1 -C 10 -alkoxy, C 1 -C 10 -alkyl, C 3 -C 10 -cycloalkyl, C 3 -C 10 -heterocyclyl comprising at least one heteroatom selected from the group consisting of N, O and S, C 5 -C 10 -aryl and C 5 -C 10 -heteroaryl comprising at least one heteroatom selected from the group consisting of N, O and S,

wherein substituents are selected from the group consisting of: F, Cl, Br, OH, CN, NH 2 and C 1 -C 10 -alkyl.

8. The process according to claim 1 , wherein the complex catalyst has formula (XVIa):

9. The process according to claim 1 , wherein Y in the complex catalyst is selected from the group consisting of H, F, Cl and Br.

10. The process according to claim 1 , wherein L 3 in the complex catalyst is CO.

11. The process according to claim 1 , wherein (—X) is selected from functional

Assignees

• Basf Se

Inventors

• Schaub Thomas
• Buschhaus Boris
• Da Silva Marion Kristina
• Schelwies Mathias
• Paciello Rocco
• Melder Johann-Peter
• Merger Martin

Classifications

• C07D207/20

  with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms · CPC title

• C07D207/02

  with only hydrogen or carbon atoms directly attached to the ring nitrogen atom · CPC title

• C07C211/09

  Diamines · CPC title

• C07C211/10

  Diaminoethanes · CPC title

• C07D211/06

  having no double bonds between ring members or between ring members and non-ring members · CPC title